Catalyst comprised of n-substituted cyclic imides and processes for preparing organic compounds with the catalyst

ABSTRACT

A catalyst of the invention includes an imide compound having a N-substituted cyclic imide skeleton represented by following Formula (I): 
                         
wherein R is a hydroxyl-protecting group. Preferred R is a hydrolyzable protecting group. R may be a group obtained from an acid by eliminating an OH group therefrom. Such acids include, for example, carboxylic acids, sulfonic acids, carbonic acid, carbamic acid, sulfuric acid, nitric acid, phosphoric acids and boric acids. The catalyst may include the imide compound and a metallic compound in combination. In the presence of the catalyst, (A) a compound capable of forming a radical is allowed to react with (B) a radical scavenging compound and thereby yields an addition or substitution reaction product of the compound (A) and the compound (B) or a derivative thereof. This catalyst can produce an organic compound with a high selectivity in a high yield as a result of, for example, an addition or substitution reaction under mild conditions.

This application is the national phase under 35 U.S.C. § 371 of PCTInternational Application No. PCT/JP02/09666 which has an Internationalfiling date of Sep. 20, 2002, which designated the United States ofAmerica.

TECHNICAL FIELD

The present invention relates to a catalyst that is useful foroxidation, nitration, carboxylation, reaction for the formation of acarbon-carbon bond, and other reactions and to a process for producingan organic compound using the catalyst.

BACKGROUND ART

An oxidation reaction is one of the most basic reactions in the field oforganic chemical industry, and various oxidation processes have beendeveloped. From the viewpoints of resources and environmental issues, acatalytic oxidation process, in which molecular oxygen or air isdirectly used as an oxidizing agent, is preferred. However, thecatalytic oxidation process generally requires high temperatures and/orhigh pressures for activation of oxygen or, alternatively, must beperformed in the co-existence of a reducing agent such as an aldehyde toproceed the reaction under mild conditions. Accordingly, such aconventional catalytic oxidation process cannot easily and efficientlyproduce an alcohol or a carboxylic acid under mild conditions.

Lower hydrocarbons such as methane and ethane are nitrated using nitricacid or nitrogen dioxide at high temperatures of from 250° C. to 300° C.However, when a hydrocarbon having a large number of carbon atoms isnitrated under the above condition, the substrate is decomposed, and atarget nitro compound cannot be obtained in a high yield. To nitratehydrocarbons, a method using mixed acid (a mixture of nitric acid andsulfuric acid) is widely employed. However, this method requires largeamounts of a strong acid in a high concentration.

Additionally, few processes are known for efficiently and directlyintroducing carboxyl groups into hydrocarbons under mild conditions.

A variety of processes are known for producing organic sulfur acids orsalts thereof. For example, processes for producing a sulfonic acidinclude a process of oxidizing a thiol or disulfide with an oxidizingagent, a process of allowing an aromatic hydrocarbon to react withanhydrous SO₃-pyridine or chlorosulfuric acid by using a Friedel-Craftsreaction, and a process of synthetically obtaining a sulfonic acid bysubjecting an unsaturated compound to free-radical addition. Theseprocesses, however, require extreme reaction conditions or inevitablyproduce large amounts of by-products. Additionally, no processes fordirectly and efficiently sulfonating non-aromatic hydrocarbons have beenknown.

Processes are known in which a variety of compounds are added tounsaturated compounds each having a carbon-carbon double bond orheteroatom-containing compounds and thereby yield useful organiccompounds. For example, when an active methylene compound such as amalonic diester is allowed to react with an olefin having an electronattractive group, such as acrylonitrile, in the presence of a base, acarbon-carbon bond is formed as a result of a nucleophilic additionreaction and thereby yields an addition product (Michael additionreaction). When two types of carbonyl compounds are treated in thepresence of an acid or a base, one carbonyl compound is nucleophilicallyadded to the other to form a carbon-carbon bond and thereby yields analdol condensate.

These processes, however, are generally performed in the presence of anacid or base and cannot be applied to compounds each having asubstituent that is susceptible to the acid or base. In addition, theseprocesses cannot allow, for example, a hydroxymethyl group, analkoxymethyl group, an acyl group or a tertiary carbon atom to directlycombine with a carbon atom constituting an unsaturated boned of anunsaturated compound or with a methine carbon atom of a bridged cycliccompound.

Addition reactions to a carbon-carbon double bond in accordance with aradical mechanism or coupling reactions to form a carbon-carbon bond arealso known. However, there are few processes that can efficiently yieldaddition or substitution reaction products or derivatives thereof byaction of, for example, molecular oxygen under mild conditions.

Some processes are known as production processes ofhydroxy-γ-butyrolactone derivatives. For example, European PatentPublication EP-A-2103686 discloses a process for synthetically obtainingpantolactone by allowing glyoxylic acid to react with isobutylene.Likewise, Japanese Unexamined Patent Application Publication No.61-282373 discloses a process for synthetically obtaining pantolactoneby allowing hydrated glyoxylic acid to react with t-butyl alcohol.Tetrahedron, 933 (1979) discloses a process for synthetically obtainingpantolactone. This process includes the steps of hydrolyzing4-hydroxy-2-methyl-5,5,5-trichloro-1-pentene to yield2-hydroxy-4-methyl-4-pentenoic acid and cyclizing this compound in thepresence of hydrochloric acid. In addition, The Chemical Society ofJapan, Spring Conference Proceedings II, pp. 1015 (1998) reports thatlight irradiation to a mixture solution containing anα-acetoxy-α,β-unsaturated carboxylic ester and 2-propanol yields acorresponding α-acetoxy-γ,γ-dimethyl-γ-butyrolactone derivative.However, each of these processes employs a material that is not easilyavailable or requires special conditions for the reaction.

Japanese Unexamined Patent Application Publications No. 8-38909 and No.9-327626 each propose an oxidation catalyst comprising an imide compoundhaving a specific structure or the imide compound in combination with,for example, a transition metal compound as a catalyst for oxidizing anorganic substrate with molecular oxygen. Japanese Unexamined PatentApplication Publication No. 11-239730 discloses a process, in which asubstrate is allowed to react with at least one reactant selected from(i) nitrogen oxides and (ii) mixtures of carbon monoxide and oxygen inthe presence of the imide compound and thereby at least one functionalgroup selected from nitro group and carboxyl group is introduced intothe substrate. PCT International Publication No. WO00/35835 discloses aprocess, in which two compounds are allowed to react with each other inthe presence of a specific imide compound and a radical generator withrespect to the imide compound and thereby yield an addition orsubstitution reaction product or an oxidized product thereof inaccordance with a radical mechanism. These processes using the imidecompounds can introduce an oxygen-atom-containing group such as hydroxylgroup, nitro group or carboxyl group into a substrate or can form acarbon-carbon bond. However, they are still insufficient in yields ofthe target compounds, stability of the catalysts or amounts of thecatalysts.

DISCLOSURE OF INVENTION

Accordingly, an object of the present invention is to provide a catalystthat can yield an organic compound with a high selectivity in a highyield as a result of, for example, an addition or substitution reactionunder mild condition and to provide a process for producing an organiccompound using the catalyst.

Another object of the present invention is to provide a catalyst thatcan introduce an oxygen-atom-containing group into an organic substrateunder mild conditions and to provide a process for producing an organiccompound using the catalyst.

Yet another object of the present invention is to provide a catalystthat is highly stable and can maintain its catalytic activity for a longtime.

A further object of the present invention is to provide a radicalreaction catalyst that exhibits high catalytic activity even in a smallamount.

Another object of the present invention is to provide a radical reactioncatalyst that is highly stable even at high temperatures.

After intensive investigations to achieve the above objects, the presentinventors have found that, when a compound capable of forming a radicalis allowed to react with a radical scavenging compound in the presenceof an imide compound having a specific structure, a correspondingaddition or substitution reaction product or a derivative thereof can beobtained under mild conditions. The present invention has beenaccomplished based on these findings.

Specifically, the present invention provides, in an aspect, a catalystincluding an imide compound having a N-substituted cyclic imide skeletonrepresented by following Formula (I):

wherein R is a hydroxyl-protecting group.

Such imide compounds include, for example, a compound represented byfollowing Formula (1):

wherein R is a hydroxyl-protecting group; R¹, R², R³, R⁴, R⁵ and R⁶ arethe same or different and are each a hydrogen atom, a halogen atom, analkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, analkoxy group, a carboxyl group, a substituted oxycarbonyl group, anacylgroup or an acyloxy group, where at least two of R¹, R², R³, R⁴, R⁵ andR⁶ may be combined with each other to form a double bond, an aromatic ornon-aromatic ring, and where at least one N-substituted cyclic imidogroup indicated in Formula (1) may further be formed on R¹, R², R³, R⁴,R⁵ and R⁶ or on the double bond, the aromatic or non-aromatic ringformed by at least two of R¹, R², R³, R⁴, R⁵ and R⁶.

The protecting group R is preferably a hydrolyzable protecting group. Rmay be a group obtained from an acid by eliminating an OH group from theacid. Such acids include, for example, carboxylic acids, sulfonic acids,carbonic acid, carbamic acid, sulfuric acid, nitric acid, phosphoricacids and boric acids.

The catalyst may include the imide compound and a metallic compound incombination.

In another aspect, the present invention provides a process forproducing an organic compound, the process including the step ofallowing (A) a compound capable of forming a radical to react with (B) aradical scavenging compound in the presence of the catalyst to yield aproduct of an addition or substitution reaction between the compound (A)and the compound (B), or a derivative thereof.

As the compound (A) capable of forming a radical, use can be made of oneselected from (A1) heteroatom-containing compounds each having acarbon-hydrogen bond at the adjacent position to the heteroatom, (A2)compounds each having a carbon-heteroatom double bond, (A3) compoundseach having a methine carbon atom, (A4) compounds each having acarbon-hydrogen bond at the adjacent position to an unsaturated bond,(A5) non-aromatic cyclic hydrocarbons, (A6) conjugated compounds, (A7)amines, (A8) aromatic compounds, (A9) straight-chain alkanes and (A10)olefins.

The radical scavenging compound (B) may be one selected from (B1)unsaturated compounds, (B2) compounds each having a methine carbon atom,(B3) compounds each containing a heteroatom and (B4)oxygen-atom-containing reactants (reacting agents). Suchoxygen-atom-containing reactants (B4) include, for example, oxygen,carbon monoxide, nitrogen oxides, sulfur oxides, and nitric acid,nitrous acid or salts thereof.

The reactions between the compound (A) capable of forming a radical andthe radical scavenging compound (B) include, for example, oxidationreactions, carboxylation reactions, nitration reactions, sulfonationreactions, coupling reactions and combinations thereof.

The process of an organic compound includes a step of allowing anaromatic compound having an alkyl group or a lower-order oxidized groupthereof combined with an aromatic ring to oxidize with oxygen to yield acorresponding aromatic carboxylic acid.

The term “addition or substitution” reaction as used herein is used in abroad meaning and also includes, for example, oxidation and sulfonation.

BEST MODE FOR CARRYING OUT THE INVENTION

[Imide Compounds]

A catalyst of the present invention comprises the imide compound havinga N-substituted cyclic imide skeleton represented by Formula (I). Theimide compound may have a plurality of the N-substituted cyclic imideskeleton represented by Formula (I) in a molecule. The imide compoundmay also have a plurality of N-oxy cyclic imide skeleton bonded throughR, which N-oxy cyclic imide skeleton is obtained from the N-substitutedcyclic imide skeleton represented by Formula (I) by eliminating Rtherefrom.

In Formula (I), the hydroxyl-protecting group represented by R includesconventional protecting groups for a hydroxyl group in the field oforganic synthesis. Such protecting groups include, but are not limitedto, alkyl groups (e.g., methyl, t-butyl, and other C₁–C₄ alkyl groups),alkenyl groups (e.g., allyl group), cycloalkyl groups (e.g., cyclohexylgroup), aryl groups (e.g., 2,4-dinitrophenyl group), aralkyl groups(e.g., benzyl, 2,6-dichlorobenzyl, 3-bromobenzyl, 2-nitrobenzyl, andtriphenylmethyl groups); substituted methyl groups (e.g., methoxymethyl,methylthiomethyl, benzyloxymethyl, t-butoxymethyl,2-methoxyethoxymethyl, 2,2,2-trichloroethoxymethyl,bis(2-chloroethoxy)methyl, and 2-(trimethylsilyl)ethoxymethyl groups),substituted ethyl groups (e.g., 1-ethoxyethyl, 1-methyl-1-methoxyethyl,1-isopropoxyethyl, 2,2,2-trichloroethyl, and 2-methoxyethyl groups),tetrahydropyranyl group, tetrahydrofuranyl group, 1-hydroxyalkyl groups(e.g., 1-hydroxyethyl, 1-hydroxyhexyl, 1-hydroxydecyl,1-hydroxyhexadecyl, and 1-hydroxy-1-phenylmethyl groups), and othergroups that can form an acetal group or hemiacetal group with a hydroxylgroup; acyl groups (e.g., formyl, acetyl, propionyl, butyryl,isobutyryl, valeryl, pivaloyl, hexanoyl, heptanoyl, octanoyl, nonanoyl,decanoyl, lauroyl, myristoyl, palmitoyl, stearoyl, and other C₁–C₂₀aliphatic acyl groups, and other aliphatic saturated or unsaturated acylgroups; acetoacetyl group; cyclopentanecarbonyl, cyclohexanecarbonyl,and other cycloalkanecarbonyl groups, and other alicyclic acyl groups;benzoyl, naphthoyl, and other aromatic acyl groups), sulfonyl groups(e.g., methanesulfonyl, ethanesulfonyl, trifluoromethanesulfonyl,benzenesulfonyl, p-toluenesulfonyl, and naphthalenesulfonyl groups),alkoxycarbonyl groups (e.g., methoxycarbonyl, ethoxycarbonyl,t-butoxycarbonyl, and other C₁–C₄ alkoxy-carbonyl groups),aralkyloxycarbonyl groups (e.g., benzyloxycarbonyl group andp-methoxybenzyloxycarbonyl group), substituted or unsubstitutedcarbamoyl groups (e.g., carbamoyl, methylcarbamoyl, and phenylcarbamoylgroups), groups obtained from inorganic acids (e.g., sulfuric acid,nitric acid, phosphoric acids, and boric acids) by eliminating an OHgroup therefrom, dialkylphosphinothioyl groups (e.g.,dimethylphosphinothioyl group), diarylphosphinothioyl groups (e.g.,diphenylphosphinothioyl group), and substituted silyl groups (e.g.,trimethylsilyl, t-butyldimethylsilyl, tribenzylsilyl, and triphenylsilylgroups).

The imide compound may have a plurality of N-oxy cyclic imide skeletonbonded through R, which N-oxy cyclic imide skeleton is obtained from theN-substituted cyclic imide skeleton represented by Formula (I) byeliminating R therefrom. In this case, R includes, but is not limitedto, oxalyl, malonyl, succinyl, glutaryl, adipoyl, phthaloyl,isophthaloyl, terephthaloyl, and other acyl groups derived frompolycarboxylic acids; carbonyl group; and methylene, ethylidene,isopropylidene, cyclopentylidene, cyclohexylidene, benzylidene, andother polyvalent hydrocarbon groups (specifically, groups that formacetal bonds with two hydroxyl groups).

Preferred Rs include, for example, groups that can form an acetal orhemiacetal with a hydroxyl group; groups (e.g., acyl groups, sulfonylgroups, alkoxycarbonyl groups, and carbamoyl groups) obtained from acids(e.g., carboxylic acids, sulfonic acids, carbonic acid, carbamic acid,sulfuric acid, phosphoric acids, and boric acids) by eliminating an OHgroup therefrom, and other hydrolyzable protecting groups that can bedeprotected by hydrolysis.

Typical examples of the imide compounds are the imide compoundsrepresented by Formula (1). Of the substituents R¹, R², R³, R⁴, R⁵ andR⁶ in the imide compounds, the halogen atom includes iodine, bromine,chlorine and fluorine atoms. The alkyl group includes, but is notlimited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl,t-butyl, hexyl, decyl, dodecyl, tetradecyl, hexadecyl, and otherstraight- or branched-chain alkyl groups each having from about 1 toabout 30 carbon atoms (especially, about 1 to about 20 carbon atoms).

The aryl group includes phenyl and naphthyl groups, for example.Illustrative cycloalkyl groups are cyclopentyl and cyclohexyl groups.Illustrative alkoxy groups are methoxy, ethoxy, isopropoxy, butoxy,t-butoxy, hexyloxy, octyloxy, decyloxy, dodecyloxy, tetradecyloxy,octadecyloxy, and other alkoxy groups each having from about 1 to about30 carbon atoms (especially, about 1 to 20 carbon atoms).

Examples of the substituted oxycarbonyl group include methoxycarbonyl,ethoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, t-butoxycarbonyl,hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl,dodecyloxycarbonyl, tetradecyloxycarbonyl, hexadecyloxycarbonyl,octadecyloxycarbonyl, and other C₁–C₃₀ alkoxycarbonyl groups(especially, C₁–C₂₀ alkoxy-carbonyl groups); cyclopentyloxycarbonyl,cyclohexyloxycarbonyl, and other cycloalkyloxycarbonyl groups(especially, 3- to 20-membered cycloalkyloxycarbonyl groups);phenyloxycarbonyl, naphthyloxycarbonyl, and other aryloxycarbonyl groups(especially, C₆–C₂₀ aryloxy-carbonyl groups); and benzyloxycarbonyl andother aralkyloxycarbonyl groups (especially, C₇–C₂₁ aralkyloxy-carbonylgroups).

The acyl group includes, but is not limited to, formyl, acetyl,propionyl, butyryl, isobutyryl, valeryl, pivaloyl, hexanoyl, heptanoyl,octanoyl, nonanoyl, decanoyl, lauroyl, myristoyl, palmitoyl, stearoyl,and other C₁–C₃₀ aliphatic acyl groups (especially, C₁–C₂₀ aliphaticacyl groups), and other aliphatic saturated or unsaturated acyl groups;acetoacetyl group; cyclopentanecarbonyl, cyclohexanecarbonyl, and othercycloalkanecarbonyl groups and other alicyclic acyl groups; benzoyl,naphthoyl, and other aromatic acyl groups.

The acyloxy group includes, but is not limited to, formyloxy, acetyloxy,propionyloxy, butyryloxy, isobutyryloxy, valeryloxy, pivaloyloxy,hexanoyloxy, heptanoyloxy, octanoyloxy, nonanoyloxy, decanoyloxy,lauroyloxy, myristoyloxy, palmitoyloxy, stearoyloxy, and other C₁–C₃₀aliphatic acyloxy groups (especially, C₁–C₂₀ aliphatic acyloxy groups),and other aliphatic saturated or unsaturated acyloxy groups;acetoacetyloxy group; cyclopentanecarbonyloxy, cyclohexanecarbonyloxy,and other cycloalkanecarbonyloxy groups and other alicyclic acyloxygroups; benzoyloxy, naphthoyloxy, and other aromatic acyloxy groups.

The substituents R¹, R², R³, R⁴, R⁵ and R⁶ may be the same or different.In Formula (1), at least two of R¹, R², R³, R⁴, R⁵ and R⁶ may becombined to form a double bond, an aromatic or non-aromatic ring. Thepreferred aromatic or non-aromatic ring has from about 5 to about 12members, and specifically from about 6 to about 10 members. The ring maybe a heterocyclic ring or condensed heterocyclic ring, but it is often ahydrocarbon ring. Such rings include, for example, non-aromaticalicyclic rings (e.g., cyclohexane ring and other cycloalkane ringswhich may have a substituent, cyclohexene ring and other cycloalkenerings which may have a substituent), non-aromatic bridged rings (e.g.,5-norbornene ring and other bridged hydrocarbon rings which may have asubstituent), benzene ring, naphthalene ring, and other aromatic rings(including condensed rings) which may have a substituent. The ringcomprises an aromatic ring in many cases. The ring may have asubstituent. Such substituents include, but are not limited to, alkylgroups, haloalkyl groups, hydroxyl group, alkoxy groups, carboxyl group,substituted oxycarbonyl groups, acyl groups, acyloxy groups, nitrogroup, cyano group, amino groups, and halogen atoms.

At least one N-substituted cyclic imido group indicated in Formula (1)may further be formed on R¹, R², R³, R⁴, R⁵ or R⁶ or on the double bondor aromatic or non-aromatic ring formed by at least two of R¹, R², R³,R⁴, R⁵ and R⁶. For example, when R¹, R², R³, R⁴, R⁵ or R⁶ is an alkylgroup having two or more carbon atoms, the N-substituted cyclic imidogroup may be formed together with the adjacent two carbon atomsconstituting the alkyl group. Likewise, when at least two of R¹, R², R³,R⁴, R⁵ and R⁶ are combined to form a double bond, the N-substitutedcyclic imido group may be formed together with the double bond. When atleast two of R¹, R², R³, R⁴, R⁵ and R⁶ are combined to form an aromaticor non-aromatic ring, the N-substituted cyclic imido group may be formedwith the adjacent two carbon atoms constituting the ring. In addition, aN-hydroxy form (a N-hydroxy cyclic imido group) of the N-substitutedcyclic imido group indicated in Formula (1), a 5-membered N-substitutedcyclic imido group corresponding to the 6-membered N-substituted cyclicimido group indicated in Formula (1) or a N-hydroxy form thereof may beformed on R¹, R², R³, R⁴, R⁵ or R⁶ or on the double bond, aromatic ornon-aromatic ring formed by at least two of R¹, R², R³, R⁴, R⁵ and R⁶.

Preferred imide compounds include compounds of the following formulae:

wherein R¹¹ to R¹⁶ are the same or different and are each a hydrogenatom, a halogen atom, an alkyl group, a aryl group, a cycloalkyl group,a hydroxyl group, an alkoxy group, a carboxyl group, a substitutedoxycarbonyl group, an acyl group or an acyloxy group, and R¹⁷ to R²² arethe same or different and are each a hydrogen atom, an alkyl group, ahaloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, asubstituted oxycarbonyl group, an acyl group, a acyloxy group, a nitrogroup, a cyano group, an amino group or a halogen atom, where adjacentgroups of R¹⁷ to R²² may be combined to form a 6-membered N-substitutedcyclic imido skeleton indicated in Formula (1b) or (1c), its N-hydroxyform, a corresponding 5-membered N-substituted cyclic imido skeleton orits N-hydroxy form; R has the same meanings as defined above.

The halogen atom, the alkyl group, the aryl group, the cycloalkyl group,the hydroxyl group, the alkoxy group, the carboxyl group, thesubstituted oxycarbonyl group, the acyl group and the acyloxy group inthe substituents R¹¹ to R¹⁶ include similar groups to correspondinggroups in the substituents R¹ to R⁶.

In the substituents R¹⁷ to R²², the alkyl group includes similar alkylgroups to those exemplified above, of which alkyl groups each havingfrom about 1 to about 6 carbon atoms are specifically preferred. Thehaloalkyl group includes trifluoromethyl group and other haloalkylgroups each having from about 1 to about 4 carbon atoms. The alkoxygroup includes similar alkoxy groups to those mentioned above, of whichlower alkoxy groups each having from about 1 to about 4 carbon atoms arespecifically preferred. The substituted oxycarbonyl group includessimilar substituted oxycarbonyl groups (e.g., alkoxycarbonyl groups,cycloalkyloxycarbonyl groups, aryloxycarbonyl groups, andaralkyloxycarbonyl groups) to those described above. The acyl groupincludes similar acyl groups (e.g., aliphatic saturated or unsaturatedacyl groups, acetoacetyl group, alicyclic acyl groups, and aromatic acylgroups) to those described above. The acyloxy group includes similaracyloxy groups (e.g., aliphatic saturated or unsaturated acyloxy groups,acetoacetyloxy group, alicyclic acyloxy groups, and aromatic acyloxygroups) to those mentioned above. The halogen atom includes fluorine,chlorine and bromine atoms. Each of the substituents R¹⁷ to R²² is oftena hydrogen atom, a lower alkyl group having from about 1 to about 4carbon atoms, a carboxyl group, a substituted oxycarbonyl group, a nitrogroup or a halogen atom.

Examples of the preferred imide compounds are N-acetoxyglutarimide,N-acetoxy-α,α-dimethylglutarimide, N-acetoxy-β,β-dimethylglutarimide,N-acetoxy-1,8-decalinedicarboximide,N,N′-diacetoxy-1,8;4,5-decalinetetracarboxdiimide,N-acetoxy-1,8-naphthalenedicarboximide (N-acetoxynaphthalimide),N,N′-diacetoxy-1,8;4,5-naphthalenetetracarboxdiimide,N-propionyloxy-1,8-naphthalenedicarboximide,N,N′-bis(propionyloxy)-1,8;4,5-naphthalenetetracarboxdiimide,N-hexanoyloxy-1,8-naphthalenedicarboximide,N,N′-bis(hexanoyloxy)-1,8;4,5-naphthalenetetracarboxdiimide, and othercompounds represented by Formula (1) where R is an acetyl group oranother acyl group; N-methoxymethyloxy-1,8-naphthalenedicarboximide,N,N′-bis(methoxymethyloxy)-1,8;4,5-naphthalenetetracarboxdiimide, andother compounds represented by Formula (1) where R is a group that canform an acetal or hemiacetal with a hydroxyl group;N-methanesulfonyloxy-1,8-naphthalenedicarboximide,N,N′-bis(methanesulfonyloxy)-1,8;4,5-naphthalenetetracarboxdiimide, andother compounds represented by Formula (1) where R is a sulfonyl group;sulfuric ester, nitric ester, phosphoric ester or boric ester ofN-hydroxy-1,8-naphthalenedicarboximide orN,N′-dihydroxy-1,8;4,5-naphthalenetetracarboxdiimide, and othercompounds represented by Formula (1) where R is a group obtained from aninorganic acid by eliminating an OH group therefrom.

Each of the imide compounds can be obtained by introducing a desiredprotecting group into a corresponding compound where R is a hydrogenatom (N-hydroxy cyclic imide compound) using a conventional reaction forthe introduction of a protecting group. For example,N-acetoxy-1,8-naphthalenedicarboximide can be obtained by allowingN-hydroxy-1,8-naphthalenedicarboximide to react with acetic anhydride orto react with an acetyl halide in the presence of a base.

The compound where R is a hydrogen atom (N-hydroxy cyclic imidecompound) can be obtained by a conventional imidization process (aprocess for the formation of an imide), such as a process that comprisesthe steps of allowing a corresponding acid anhydride to react withhydroxylamine for ring-opening of an acid anhydride group, and closingthe ring to form an imide.

Typically preferred imide compounds can be obtained by introducing aprotecting group into the hydroxyl group of N-hydroxyglutarimide,N-hydroxy-1,8-naphthalenedicarboximide,N,N′-dihydroxy-1,8;4,5-naphthalenetetracarboxdiimide, and otherN-hydroxyimide compounds derived from alicyclic polycarboxylicanhydrides or aromatic polycarboxylic anhydrides.

Each of the imide compounds each having the N-substituted cyclic imideskeleton represented by Formula (I) can be used alone or in combinationin a reaction. The imide compound may be formed in the reaction system.The imide compound having the N-substituted cyclic imide skeletonrepresented by Formula (I) can be used in combination with acorresponding N-hydroxy cyclic imide compound (a compound where R is ahydrogen atom).

The amount of the imide compound according to the present invention canbe selected with in a wide range andis, for example, from about0.0000001 to about 1 mole, preferably from about 0.000001 to about 0.5mole, more preferably from about 0.00001 to about 0.4 mole, and oftenfrom about 0.0001 to about 0.35 mole, relative to 1 mole of a reactioncomponent (substrate)

[Promoter (Co-catalyst)]

According to the invention, a promoter (co-catalyst) can be used incombination with the imide compound. Such promoters include, forexample, metallic compounds. By using the imide compound in combinationwith the metallic compound, the rate and selectivity of the reaction canbe improved.

Metallic elements constituting the metallic compounds are notspecifically limited and are often metallic elements of the Groups 2 to15 of the Periodic Table of Elements. The term “metallic element” asused herein also includes boron B. Examples of the metallic elementsinclude, of the Periodic Table of Elements, Group 2 elements (e.g., Mg,Ca, Sr and Ba), Groups 3elements (e.g., Sc, lanthanoid elements andactinoid elements), Group 4 elements (e.g., Ti, Zr and Hf), Group 5elements (e.g., V), Group 6 elements (e.g., Cr, Mo and W), Group 7elements (e.g., Mn), Group 8 elements (e.g., Fe and Ru), Group 9elements (e.g., Co and Rh), Group 10 elements (e.g., Ni, Pd and Pt),Group 11 elements (e.g., Cu), Group 12 elements (e.g., Zn), Groups 13elements (e.g., B, Al and In), Group 14 elements (e.g., Sn and Pb), andGroup 15 elements (e.g., Sb and Bi). Preferred metallic elements includetransition metal elements (elements of Groups 3 to 12 of the PeriodicTable of Elements). Among them, elements of the Groups 5 to 11 of thePeriodic Table of Elements are preferred, of which elements of Groups 5to 9 are typically preferred. Especially, V, Mo, Mn and Co arepreferred. The valency of the metallic element is not specificallylimited, and is from about 0 to about 6 in many cases.

Such metallic compounds include, but are not limited to, elementarysubstances, hydroxides, oxides (including complex oxides), halides(fluorides, chlorides, bromides and iodides), salts of oxoacids (e.g.,nitrates, sulfates, phosphates, borates, and carbonates), salts ofisopolyacids, salts of heteropolyacids, and other inorganic compounds ofthe aforementioned metallic elements; salts of organic acids (e.g.,acetates, propionates, prussiates, naphthenates, orstearates),complexes, and other organic compounds of the metallic elements. Ligandsfor constituting the complexes include OH (hydroxo), alkoxy (e.g.,methoxy, ethoxy, propoxy, andbutoxy), acyl (e.g., acetyl and propionyl),alkoxycarbonyl (e.g., methoxycarbonyl and ethoxycarbonyl),acetylacetonato, cyclopentadienyl group, halogenatoms (e.g., chlorineand bromine), CO, CN, oxygen atom, H₂O (aquo), phosphines(triphenylphosphine and other triarylphosphines) and other phosphoruscompounds, NH₃ (ammine), NO, NO₂ (nitro), NO₃ (nitrato),ethylenediamine, diethylenetriamine, pyridine, phenanthroline, and othernitrogen-containing compounds.

Specific examples of the metallic compounds include, by taking cobaltcompounds as an example, cobalt hydroxide, cobalt oxide, cobaltchloride, cobalt bromide, cobalt nitrate, cobalt sulfate, cobaltphosphate, and other inorganic compounds; cobalt acetate, cobaltnaphthenate, cobalt stearate, and other salts of organic acids;acetylacetonatocobalt, and other complexes, and other divalent ortrivalent cobalt compounds. Illustrative vanadium compounds include, butare not limited to, vanadium hydroxide, vanadium oxide, vanadiumchloride, vanadyl chloride, vanadium sulfate, vanadyl sulfate, sodiumvanadate, and other inorganic compounds; acetylacetonatovanadium,vanadyl acetylacetonato, and other complexes, and other vanadiumcompounds having a valence of from 2 to 5. Examples of compounds of theother metallic elements include compounds corresponding to theabove-mentioned cobalt or vanadium compounds. Each of these metalliccompounds can be used alone or in combination. Specifically, thecombination use of a cobalt compound with a manganese compoundsignificantly increases the reaction rate in many cases. The combinationuse of plural types of metallic compounds having different valances(e.g., a divalent metallic compound in combination with a trivalentmetallic compound) is also preferred.

The amount of the metallic compound is, for example, from about 0.001 toabout 10 moles and preferably from about 0.005 to about 3 moles,relative to 1 mole of the imide compound, and is, for example, fromabout 0.00001% by mole to about 10% by mole and preferably from about0.1% by mole to about 5% by mole, relative to 1 mole of the reactioncomponent (substrate).

The promoters for use in the present invention also include organicsalts each composed of a polyatomic cation or a polyatomic anion and itscounter ion, which polyatomic cation or anion contains a Group 15 orGroup 16 element of the Periodic Table of Elements having at least oneorganic group bonded thereto. By using the organic salts as thepromoters, the rate and selectivity of the reaction can further beimproved.

In the organic salts, the Group 15 elements of the Periodic Table ofElements include N, P, As, Sb, and Bi, and the Group 16 elements of thePeriodic Table of Elements include, for example, O, S, Se and Te.Preferred elements are N, P, As, Sb and S, of which N, P and S aretypically preferred.

The organic groups to be combined with atoms of the elements include,but are not limited to, hydrocarbon groups which may have a substituent,and substituted oxy groups. The hydrocarbon groups include, but are notlimited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl,t-butyl, pentyl, hexyl, octyl, decyl, tetradecyl, hexadecyl, octadecyl,allyl, and other straight- or branched-chain aliphatic hydrocarbongroups (alkyl groups, alkenyl groups and alkynyl groups) each havingfrom about 1 to about 30 carbon atoms (preferably from about 1 to about20 carbon atoms); cyclopentyl, cyclohexyl, and other alicyclichydrocarbon groups each having from about 3 to about 8 carbon atoms; andphenyl, naphthyl, and other aromatic hydrocarbon groups each having fromabout 6 to about 14 carbon atoms. Substituents which the hydrocarbongroups may have include, but are not limited to, halogen atoms, oxogroup, hydroxyl group, substituted oxy groups (e.g., alkoxy groups,aryloxy groups, and acyloxy groups), carboxyl group, substitutedoxycarbonyl groups, substituted or unsubstituted carbamoyl groups, cyanogroup, nitro group, substituted or unsubstituted amino groups, alkylgroups (e.g., methyl, ethyl, and other C₁–C₄ alkyl groups), cycloalkylgroups, aryl groups (e.g., phenyl and naphthyl groups), and heterocyclicgroups. The preferred hydrocarbon groups include, for example, alkylgroups each having from about 1 to about 30 carbon atoms, and aromatichydrocarbon groups (especially, phenyl or naphthyl group) each havingfrom about 6 to about 14 carbon atoms. The substituted oxy groupsinclude, but are not limited to, alkoxy groups, aryloxy groups andaralkyloxy groups.

Examples of the organic salts include organic ammonium salts, organicphosphonium salts, organic sulfonium salts, and other organic oniumsalts. Such organic ammonium salts include tetramethylammonium chloride,tetraethylammonium chloride, tetrabutylammonium chloride,tetrahexylammonium chloride, trioctylmethylammonium chloride,triethylphenylammonium chloride, tributyl(hexadecyl)ammonium chloride,di(octadecyl)dimethylammonium chloride, and other quaternary ammoniumchlorides, and corresponding quaternary ammonium bromides, and otherquaternary ammonium salts each having four hydrocarbon groups combinedwith a nitrogen atom; dimethylpiperidinium chloride, hexadecylpyridiniumchloride, methylquinolinium chloride, and other cyclic quaternaryammonium salts. Examples of the organic phosphonium salts includetetramethylphosphonium chloride, tetrabutylphosphonium chloride,tributyl(hexadecyl)phosphonium chloride, triethylphenylphosphoniumchloride, and other quaternary phosphonium chlorides, and correspondingquaternary phosphonium bromides, and other quaternary phosphonium saltseach having four hydrocarbon groups combined with a phosphorus atom.Examples of the organic sulfonium salts include triethylsulfoniumiodide, ethyldiphenylsulfonium iodide, and other sulfonium salts eachhaving three hydrocarbon groups combined with a sulfur atom.

The organic salts also include methanesulfonates, ethanesulfonates,octanesulfonates, dodecanesulfonates, and other alkyl-sulfonates (e.g.,C₆–C₁₈ alkyl-sulfonates); benzenesulfonates, p-toluenesulfonates,naphthalenesulfonates, decylbenzenesulfonates, dodecylbenzenesulfonates,and other aryl-sulfonates which may be substituted with an alkyl group(e.g., C₆–C₁₈ alkyl-arylsulfonates); sulfonic acid type ion exchangeresins (ion exchangers); and phosphonic acid type ion exchange resins(ion exchangers).

The amount of the organic salt is, for example, from about 0.001 toabout 0.1 mole and preferably from about 0.005 to about 0.08 mole,relative to 1 mole of the imide compound.

The promoters for use in the present invention also include strong acids(e.g., compounds each having a pKa of less than or equal to 2 at 25°C.). Preferred strong acids include, for example, hydrogen halides,hydrohalogenic acids, sulfuric acid and heteropolyacids. The amount ofthe strong acid is, for example, from about 0.001 to about 3 molesrelative to 1 mole of the imide compound.

The promoters for use in the present invention also include compoundseach having a carbonyl group combined with an electron attractive group.Such compounds each having a carbonyl group combined with an electronattractive group include, for example, hexafluoroacetone,trifluoroacetic acid, pentafluorophenyl (methyl) ketone,pentafluorophenyl (trifluoromethyl) ketone, and benzoic acid. The amountof this compound is, for example, from about 0.0001 to about 3 molesrelative to 1 mole of the reaction component (substrate).

According to the invention, the reaction system may include a radicalgenerator or a radical reaction accelerator. Such components include,but are not limited to, halogens (e.g., chlorine and bromine), peracids(e.g., peracetic acid and m-chloroperbenzoic acid), peroxides (e.g.,hydrogen peroxide, t-butyl hydroperoxide (TBHP), and otherhydroperoxides), nitric acid, nitrous acid or salts thereof, nitrogendioxide, benzaldehyde and other aldehydes. The existence of such acomponent in the system enhances a reaction in some cases. The amount ofthe aforementioned component is, for example, from about 0.001 to about3 moles relative to 1 mole of the imide compound.

The catalysts of the present invention are useful as, for example,radical reaction catalysts. The catalysts of the present inventionexhibit similar catalytic activities to reactions in which the compounds(5-membered N-hydroxy cyclic imide compounds), where a groupcorresponding to R in Formula (I) is a hydrogen atom and atomic number(member) constituting a ring is 5, exhibit catalytic activities. Inaddition, the catalysts of the present invention have significantadvantages such that (i) they can maintain the catalytic activities fora long time, (ii) they can exhibit high catalytic activities even in asmall amount, and (iii) they can maintain catalytic activities even athigh temperatures, as compared with the 5-membered N-hydroxy cyclicimide compounds. Accordingly, the catalysts of the present invention canbe applied to all the reactions, in which the 5-membered N-hydroxycyclic imide compounds exhibit catalytic activities, and can yieldgreater advantages than the case when the 5-membered N-hydroxy cyclicimide compounds are used as catalysts.

Examples of reactions, in which the catalysts of the present inventionexhibit catalytic activities, include reactions described in thefollowing literature relating to the catalytic 5-membered N-hydroxycyclic imide compounds: Japanese Unexamined Patent ApplicationPublications No. 8-38909, No. 9-327626, No. 10-286467, No. 10-316610,No. 10-309469, No. 10-316625, No. 11-239730, No. 10-310543, No.11-49764, No. 11-106377, No. 11-226416, No. 11-228484, No. 11-228481,No. 11-315036, No. 11-300212, No. 11-335304, No. 2000-212116, No.2000-219650, No. 2000-219652 and No. 2000-256304, PCT InternationalPublications No. WO99/50204, No. WO00/35835, No. WO00/46145 and No.WO00/61665, Japanese Patent Applications No. 11-136339, No. 11-254977,No. 11-372177, No. 2000-648, No. 2000-58054, No. 2000-67682, No.2000-67679, No. 2000-67680, No. 2000-157356, No. 2000-176494, No.2000-179185, No. 2000-209205, No. 2000-345822, No. 2000-345823, and No.2000-345824.

For example, (A) a compound capable of forming a radical is allowed toreact with (B) a radical scavenging compound in the presence of thecatalyst of the present invention and thereby yields an addition orsubstitution reaction product between the compound (A) and the compound(B) or a derivative thereof.

[Compounds (A) Capable of Forming Radical]

Such compounds (A) capable of forming a radical are not specificallylimited as long as they can form a stable radical and include, forexample, (A1) heteroatom-containing compounds each having acarbon-hydrogen bond at the adjacent position to the heteroatom, (A2)compounds each having a carbon-heteroatom double bond, (A3) compoundseach having a methine carbon atom, (A4) compounds each having acarbon-hydrogen bond at the adjacent position to an unsaturated bond,(A5) non-aromatic cyclic hydrocarbons, (A6) conjugated compounds, (A7)amines, (A8) aromatic compounds, (A9) straight-chain alkanes and (A10)olefins.

These compounds may have various substituents within a range notadversely affecting the reaction. Such substituents include, but are notlimited to, halogen atoms, hydroxyl group, mercapto group, oxo group,substituted oxy groups (e.g., alkoxy groups, aryloxy groups, and acyloxygroups), substituted thio groups, carboxyl group, substitutedoxycarbonyl groups, substituted or unsubstituted carbamoyl groups, cyanogroup, nitro group, substituted or unsubstituted amino groups, sulfogroup, alkyl groups, alkenyl group, alkynyl groups, alicyclichydrocarbon groups, aromatic hydrocarbon groups, and heterocyclicgroups.

The compounds (A) capable of forming a radical act as radical donativecompounds in the reaction in question.

The heteroatom-containing compounds (A1) each having a carbon-hydrogenbond at the adjacent position to the heteroatom include, for example,(A1-1) primary or secondary alcohols or primary or secondary thiols,(A1-2) ethers each having a carbon-hydrogen bond at the adjacentposition to an oxygen atom, or sulfides each having a carbon-hydrogenbond at the adjacent position to a sulfur atom, (A1-3) acetals(including hemiacetals) each having a carbon-hydrogen bond at theadjacent position to an oxygen atom, or thioacetals (includingthiohemiacetals) each having a carbon-hydrogen bond at the adjacentposition to a sulfur atom.

The primary or secondary alcohols in the compounds (A1-1) include a widevariety of alcohols. These alcohols may be whichever of monohydric,dihydric and polyhydric alcohols.

Such primary alcohols include, but are not limited to, methanol,ethanol, 1-propanol, 1-butanol, 2-methyl-1-propanol, 1-pentanol,1-hexanol, 1-octanol, 1-decanol, 1-hexadecanol, 2-buten-1-ol, ethyleneglycol, trimethylene glycol, hexamethylene glycol, pentaerythritol, andother saturated or unsaturated aliphatic primary alcohols each havingfrom about 1 to about 30 (preferably from about 1 to about 20, and morepreferably from about 1 to about 15) carbon atoms; cyclopentylmethylalcohol, cyclohexylmethyl alcohol, 2-cyclohexylethyl alcohol, and othersaturated or unsaturated alicyclic primary alcohols; benzyl alcohol,2-phenylethyl alcohol, 3-phenylpropyl alcohol, cinnamyl alcohol, andother aromatic primary alcohols; and 2-hydroxymethylpyridine, and otherheterocyclic alcohols.

Typical secondary alcohols include, but are not limited to, 2-propanol,s-butyl alcohol, 2-pentanol, 3-pentanol, 3,3-dimethyl-2-butanol,2-octanol, 4-decanol, 2-hexadecanol, 2-penten-4-ol, 1,2-propanediol,2,3-butanediol, 2,3-pentanediol, and other vicinal diols, and othersaturated or unsaturated aliphatic secondary alcohols each having fromabout 3 to about 30 (preferably from about 3 to about 20, and morepreferably from about 3 to about 15) carbon atoms; 1-cyclopentylethanol,1-cyclohexylethanol, and other secondary alcohols each having analiphatic hydrocarbon group and an alicyclic hydrocarbon (e.g.,acycloalkyl group) combined with a carbon atom that is combined with ahydroxyl group; cyclobutanol, cyclopentanol, cyclohexanol, cyclooctanol,cyclododecanol, 2-cyclohexen-1-ol, 2-adamantanol, 2-adamantanols eachhaving from one to four hydroxyl groups at the bridgehead positions,2-adamantanols each having an oxo group on an adamantane ring, and othersaturated or unsaturated alicyclic secondary alcohols (including bridgedcyclic secondary alcohols) each having from about 3 to about 20 members(preferably from about 3 to about 15 members, more preferably from about5 to about 15 members, and typically from about 5 to about 8 members);1-phenylethanol, 1-phenylpropanol, 1-phenylmethylethanol,diphenylmethanol, and other aromatic secondary alcohols; and1-(2-pyridyl)ethanol, and other heterocyclic secondary alcohols.

Typical alcohols further include, for example, 1-adamantanemethanol,α-methyl-1-adamantanemethanol, α-ethyl-1-adamantanemethanol,α-isopropyl-1-adamantanemethanol,3-hydroxy-α-methyl-1-adamantanemethanol,3-carboxy-α-methyl-1-adamantanemethanol,α-methyl-3a-perhydroindenemethanol, α-methyl-4a-decalinmethanol,8a-hydroxy-α-methyl-4a-decalinmethanol,α-methyl-4a-perhydrofluorenemethanol,α-methyl-4a-perhydroanthracenemethanol,α-methyl-8a-perhydrophenanthrenemethanol,α-methyl-2-tricyclo[5.2.1.0^(2,6)]decanemethanol,6-hydroxy-α-methyl-2-tricyclo[5.2.1.0^(2,6)]decanemethanol,α-methyl-2a-perhydroacenaphthenemethanol,α-methyl-3a-perhydrophenalenemethanol, α-methyl-1-norbornanemethanol,α-methyl-2-norbornene-1-methanol, and other alcohols each having abridged cyclic hydrocarbon group, such as compounds each having abridged cyclic hydrocarbon group combined with a carbon atom that iscombined with a hydroxyl group.

Preferred alcohols include secondary alcohols and the alcohols eachhaving a bridged cyclic hydrocarbon group. Such preferred secondaryalcohols include 2-propanol, s-butyl alcohol, and other aliphaticsecondary alcohols; 1-cyclohexyl ethanol, and other secondary alcoholseach having an aliphatic hydrocarbon group (e.g., a C₁–C₄ alkyl group ora C₆–C₁₄ aryl group) and a non-aromatic carbocyclic group (e.g., aC₃–C₁₅ cycloalkyl group or a cycloalkenyl group) combined with a carbonatom that is combined with a hydroxyl group; cyclopentanol,cyclohexanol, 2-adamantanol, and other alicyclic secondary alcohols eachhaving from about 3 to 15members; 1-phenylethanol, and other aromaticsecondary alcohols.

The primary or secondary thiols in the compounds (A1-1) include thiolscorresponding to the primary or secondary alcohols.

The ethers each having a carbon-hydrogen bond at the adjacent positionto an oxygen atom in the compounds (A1-2) include, but are not limitedto, dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether,dibutyl ether, methyl ethyl ether, methyl butyl ether, ethyl butylether, diallyl ether, methyl vinyl ether, ethyl allyl ether, and otheraliphatic ethers; anisole, phenetole, dibenzyl ether, phenyl benzylether, and other aromatic ethers; and dihydrofuran, tetrahydrofuran,pyran, dihydropyran, tetrahydropyran, morpholine, chroman, isochroman,and other cyclic ethers to which an aromatic or non-aromatic ring may becondensed.

The sulfides each having a carbon-hydrogen bond at the adjacent positionto a sulfur atom in the compounds (A1-2) include sulfides correspondingto the ethers each having a carbon-hydrogen bond at the adjacentposition to an oxygen atom.

The acetals each having a carbon-hydrogen bond at the adjacent positionto an oxygen atom in the compounds (A1-3) include, for example, acetalsderived from aldehydes and alcohols or acid anhydrides. Such acetalsinclude cyclic acetals and acyclic acetals. The aldehydes include, butare not limited to, formaldehyde, acetaldehyde, propionaldehyde,butyraldehyde, isobutyraldehyde, pentanal, hexanal, decanal, and otheraliphatic aldehydes; cyclopentanecarbaldehyde, cyclohexanecarbaldehyde,and other alicyclic aldehydes; benzaldehyde, phenylacetaldehyde, andother aromatic aldehydes. The alcohols include, but are not limited to,methanol, ethanol, 1-propanol, 1-butanol, benzyl alcohol, and othermonohydric alcohols; ethylene glycol, propylene glycol, 1,3-propanediol,2,2-dibromo-1,3-propanediol, and other dihydric alcohols. Typicalacetals are, for example, 1,3-dioxolane, 2-methyl-1,3-dioxolane,2-ethyl-1,3-dioxolane, and other 1,3-dioxolane compounds;2-methyl-1,3-dioxane, and other 1,3-dioxane compounds; acetaldehydedimethyl acetal, and other dialkyl acetal compounds.

The thioacetals each having a carbon-hydrogen bond at the adjacentposition to a sulfur atom in the compounds (A1-3) include thioacetalscorresponding to the acetals each having a carbon-hydrogen bond at theadjacent position to an oxygen atom.

The compounds (A2) each having a carbon-heteroatom double bond include,for example, (A2-1) compounds each containing a carbonyl group, (A2-2)compounds each containing a thiocarbonyl group, and (A2-3) imines. Thecompounds (A2-1) each containing a carbonyl group include ketones andaldehydes. Such ketones and aldehydes include, but are not limited to,acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutylketone, methyl s-butyl ketone, methyl t-butyl ketone, 3-pentanone,methyl decyl ketone, methyl isopropyl ketone, isopropylbutyl ketone,methyl vinyl ketone, methyl isopropenyl ketone, methyl cyclohexylketone, acetophenone, methyl 2-methylphenyl ketone, methyl 2-pyridylketone, cyclohexyl phenyl ketone, and other chain ketones;cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone,4-methylcyclohexanone, 4-chlorocyclohexanone, isophorone,cycloheptanone, cyclooctanone, cyclodecanone, cyclododecanone,cyclopentadecanone, 1,3-cyclohexanedione, 1,4-cyclohexanedione,1,4-cyclooctanedione, 2,2-bis(4-oxocyclohexyl)propane,bis(4-oxocyclohexyl)methane, 4-(4-oxocyclohexyl)cyclohexanone,2-adamantanone, and other cyclic ketones; biacetyl (2,3-butanedione),2,3-pentanedione, 3,4-hexanedione, bibenzoyl (benzil), acetylbenzoyl,cyclopentane-1,2-dione, cyclohexane-1,2-dione, and other 1,2-dicarbonylcompounds (e.g., α-diketones); acetoin, benzoin, and otherα-keto-alcohols; acetaldehyde, propionaldehyde, butanal, hexanal,succinaldehyde, glutaraldehyde, adipaldehyde, and other aliphaticaldehydes; cyclohexyl aldehyde, citral, citronellal, and other alicyclicaldehydes; benzaldehyde, carboxybenzaldehyde, nitrobenzaldehyde,cinnamaldehyde, salicylaldehyde, anisaldehyde, phthalaldehyde,isophthalaldehyde, terephthalaldehyde, and other aromatic aldehydes; andfurfural, nicotinaldehyde, and other heterocyclic aldehydes.

The compounds (A2-2) each having a thiocarbonyl group include compoundseach having a thiocarbonyl group corresponding to the compounds (A2-1)each having a carbonyl group.

The imines (A2-3) include, but are not limited to, imines (includingoximes and hydrazones) derived from the compounds (A2-1) each having acarbonyl group with ammonia or amines. Such amines include, for example,methylamine, ethylamine, propylamine, butylamine, hexylamine,benzylamine, cyclohexylamine, aniline, and other amines; hydroxylamine,O-methylhydroxylamine and other hydroxylamines; hydrazine,methylhydrazine, phenylhydrazine, and other hydrazines.

The compounds (A3) each having a methine carbon atom include, forexample, (A3-1) cyclic compounds each having a methine group (i.e., amethine carbon-hydrogen bond) as a constitutional unit of a ring, and(A3-2) chain compounds each having a methine carbon atom.

The cyclic compounds (A3-1) include, for example, (A3-1a) bridged cycliccompounds each having at least one methine group, and (A3-1b)non-aromatic cyclic compounds (e.g., alicyclic hydrocarbons) each havinga hydrocarbon group combined with a ring. The bridged cyclic compoundsalso include compounds, in which two rings commonly possess two carbonatoms, such as hydrogenated products of condensed polycyclic aromatichydrocarbons.

The bridged cyclic compounds (A3-1a) include, but are not limited to,decalin, bicyclo[2.2.0]hexane, bicyclo[2.2.2]octane,bicyclo[3.2.1]octane, bicyclo[4.3.2]undecane, bicyclo[3.3.3]undecane,thujone, carane, pinane, pinene, bornane, bornylene, norbornane,norbornene, camphor, camphoric acid, camphene, tricyclene,tricyclo[5.2.1.0^(3,8)]decane, tricyclo[4.2.1.1^(2,5)]decane,exotricyclo[5.2.1.0^(2,6)]decane, endotricyclo[5.2.1.0^(2,6)]decane,tricyclo[4.3.1.1^(2,5)]undecane, tricyclo[4.2.2.1^(2,5)]undecane,endotricyclo[5.2.2.0^(2,6)]undecane, adamantane, 1-adamantanol,1-chloroadamantane, 1-methyladamantane, 1,3-dimethyladamantane,1-methoxyadamantane, 1-carboxyadamantane, 1-methoxycarbonyladamantane,1-nitroadamantane, tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodecane,perhydroanthracene, perhydroacenaphthene, perhydrophenanthrene,perhydrophenalene, perhydroindene, quinuclidine, and other bridgedcyclic hydrocarbons or bridged heterocyclic compounds each having two tofour rings, and derivatives thereof. These bridged cyclic compounds eachhave a methine carbon atom at a bridgehead position (corresponding to ajunction position when two rings commonly possess two atoms).

The non-aromatic cyclic compounds (A3-1b) each having a hydrocarbongroup combined with a ring include, but are not limited to,1-methylcyclopentane, 1-methylcyclohexane, limonene, menthene, menthol,carbomenthone, menthone, and other alicyclic hydrocarbons each havingfrom about 3 to about 15 members and having a hydrocarbon group (e.g.,an alkyl group) combined with its ring, and their derivatives. Thehydrocarbon group just mentioned above contains from about 1 to about 20(preferably from about 1 to about 10) carbon atoms. The non-aromaticcyclic compounds (A3-1b) each having a hydrocarbon group combined with aring have a methine carbon atom at the bonding position between the ringand the hydrocarbon group.

The chain compounds (A3-2) each having a methine carbon atom include,but are not limited to, chain hydrocarbons each having a tertiary carbonatom, such as isobutane, isopentane, isohexane, 3-methylpentane,2,3-dimethylbutane, 2-methylhexane, 3-methylhexane, 3,4-dimethylhexane,3-methyloctane, and other aliphatic hydrocarbons each having from about4 to about 20 (preferably from about 4 to about 10) carbon atoms, andderivatives thereof.

The compounds (A4) each having a carbon-hydrogen bond at the adjacentposition to an unsaturated bond include, for example, aromatic compoundseach having a methyl group or methylene group at the adjacent positionto an aromatic ring (a “benzyl position”), and (A4-2) non-aromaticcompounds each having a methyl group or methylene group at the adjacentposition to an unsaturated bond (e.g., a carbon-carbon triple bond or acarbon-oxygen double bond).

In the aromatic compounds (A4-1), the aromatic ring may be either of anaromatic hydrocarbon ring or an aromatic heterocyclic ring. Sucharomatic hydrocarbon rings include, but are not limited to, benzenering, condensed carbocyclic rings (e.g., naphthalene, azulene, indacene,anthracene, phenanthrene, triphenylene, pyrene, and other condensedcarbocyclic rings in which two to ten 4- to 7-membered carbocyclic ringsare condensed). The aromatic heterocyclic rings include, but are notlimited to, heterocyclic rings each containing an oxygen atom asaheteroatom (e.g., furan, oxazole, isoxazole and other 5-membered rings;4-oxo-4H-pyran and other 6-membered rings; benzofuran, isobenzofuran,4-oxo-4H-chromene and other condensed rings), heterocyclic rings eachcontaining a sulfur atom as a heteroatom (e.g., thiophene, thiazole,isothiazole, thiadiazole, and other 5-membered rings; 4-oxo-4H-thiopyranand other 6-membered rings; benzothiophene and other condensed rings),heterocyclic rings each containing a nitrogen atom as a heteroatom(e.g., pyrrole, pyrazole, imidazole, triazole, and other 5-memberedrings; pyridine, pyridazine, pyrimidine, pyrazine, and other 6-memberedrings; indole, quinoline, acridine, naphthyridine, quinazoline, purine,and other condensed rings).

The methylene group at the adjacent position to the aromatic ring may bea methylene group constituting a non-aromatic ring condensed to thearomatic ring. In the aromatic compounds (A4-1), both methyl group andmethylene group may exist at the adjacent position to the aromatic ring.

The aromatic compounds each having a methyl group at the adjacentposition to an aromatic ring include, but are not limited to, aromatichydrocarbons each having from about one to about six methyl groupssubstituted on the aromatic ring (e.g., toluene, xylene,1-ethyl-4-methylbenzene, 1-ethyl-3-methylbenzene,1-isopropyl-4-methylbenzene, 1-t-butyl-4-methylbenzene,1-methoxy-4-methylbenzene, mesitylene, pseudocumene, durene,methylnaphthalene, dimethylnaphthalene, methylanthracene,4,4′-dimethylbiphenyl, tolualdehyde, dimethylbenzaldehyde,trimethylbenzaldehyde, toluic acid, trimethylbenzoic acid, anddimethylbenzoic acid), and heterocyclic compounds each having from aboutone to about six methyl groups substituted on a heterocyclic ring (e.g.,2-methylfuran, 3-methylfuran, 3-methythiophene, 2-methylpyridine,3-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine,2,4,6-trimethylpyridine, 4-methylindole, 2-methylquinoline, and3-methylquinoline).

The aromatic compounds each having a methylene group at the adjacentposition to an aromatic ring include, but are not limited to, aromatichydrocarbons each having an alkyl group or substituted alkyl grouphaving two or more carbon atoms (e.g., ethylbenzene, propylbenzene,1,4-diethylbenzene, and diphenylmethane), aromatic heterocycliccompounds each having an alkyl group or substituted alkyl group havingtwo or more carbon atoms (e.g., 2-ethylfuran, 3-propylthiophene,4-ethylpyridine, and 4-butylquinoline), and compounds each having anon-aromatic ring condensed to an aromatic ring, which non-aromatic ringhas a methylene group at the adjacent position to the aromatic ring(e.g., dihydronaphthalene, indene, indan, tetralin, fluorene,acenaphthene, phenalene, indanone, and xanthene).

The non-aromatic compounds (A4-2) each having a methyl group ormethylene group at the adjacent position to an unsaturated bond include,for example, (A4-2a) chain unsaturated hydrocarbons each having a methylgroup or methylene group at an “allyl position”, and (A4-2b) compoundseach having a methyl group or methylene group at the adjacent positionto a carbonyl group.

The chain unsaturated hydrocarbons (A4-2a) include, but are not limitedto, propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 2-hexene,1,5-hexadiene, 1-octene, 3-octene, undecatrines, and other chainunsaturated hydrocarbons each having from about 3 to about 20 carbonatoms. The compounds (A4-2b) include, but are not limited to, ketones(e.g., acetone, methyl ethyl ketone, 3-pentanone, acetophenone, andother chain ketones; and cyclohexanone and other cyclic ketones),carboxylic acids or derivatives thereof (e.g., acetic acid, propionicacid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid,phenylacetic acid, malonic acid, succinic acid, glutaric acid, andesters of these acids).

The non-aromatic cyclic hydrocarbons (A5) include (A5-1) cycloalkanesand (A5-2) cycloalkenes.

The cycloalkanes (AS-1) include, but are not limited to, compounds eachhaving a 3- to 30-membered cycloalkane ring, such as cyclopropane,cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane,cyclononane, cyclodecane, cyclododecane, cyclotetradecane,cyclohexadecane, cyclotetracosane, cyclotriacontane, and derivatives ofthese compounds. Preferred cycloalkane rings include 5- to 30-memberedcycloalkane rings, of which 5- to 20-membered cycloalkane rings aretypically preferred.

The cycloalkenes (A5-2) include, but are not limited to, compounds eachhaving a 3- to 30-membered cycloalkene ring, such as cyclopropene,cyclobutene, cyclopentene, cyclooctene, cyclohexene,1-methyl-cyclohexene, isophorone, cycloheptene, cyclododecene, as wellas cyclopentadiene, 1,3-cyclohexadiene, 1,5-cyclooctadiene, and othercycloalkadienes, cyclooctatriene and other cycloalkatrienes, andderivatives of these compounds. Preferred cyclalkenes include compoundseach having a 3- to 20-membered ring, of which compounds each having a3- to 12-membered ring are typically preferred.

The conjugated compounds (A6) include, for example, (A6-1) conjugateddienes, (A6-2) α,β-unsaturated nitriles, and (A6-3) α,β-unsaturatedcarboxylic acids or derivatives (e.g., esters, amides and acidanhydrides) thereof.

The conjugated dienes (A6-1) include, but are not limited to, butadiene,isoprene, 2-chlorobutadiene, and 2-ethylbutadiene. The conjugated dienes(A6-1) also include, herein, vinyl acetylene and other compounds inwhich a double bond and a triple bond are conjugated.

The α,β-unsaturated nitriles (A6-2) include, for example,(meth)acrylonitrile. The α,β-unsaturated carboxylic acids or derivativesthereof (A6-3) include, but are not limited to, (meth)acrylic acid;methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate,butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and other(meth)acrylic esters; (meth)acrylamide, N-methylol(meth)acrylamide andother (meth)acrylamide derivatives.

The amines (A7) include, but are not limited to, primary or secondaryamines such as methylamine, ethylamine, propylamine, butylamine,dimethylamine, diethylamine, dibutylamine, ethylenediamine,1,4-butanediamine, hydroxylamine, ethanolamine, and other aliphaticamines; cyclopentylamine, cyclohexylamine, and other alicyclic amines;benzylamine, toluidine, and other aromatic amines; pyrrolidine,piperidine, piperazine, indoline, and other cyclic amines to which anaromatic or non-aromatic ring may be condensed.

The aromatic hydrocarbons (A8) include, but are not limited to, benzene,naphthalene, acenaphthylene, phenanthrene, anthracene, naphthacene,aceanthrylene, triphenylene, pyrene, chrysene, naphthacene, picene,perylene, pentacene, coronene, pyranthrene, ovalene, and other aromaticcompounds each having at least one benzene ring. Of these aromatichydrocarbons, preferred are condensed polycyclic aromatic compounds inwhich at least a plurality of benzene rings (e.g., two to ten benzenerings) are condensed. These aromatic hydrocarbons may each have at leastone substituent. Examples of such aromatic hydrocarbons each having asubstituent are 2-chloronaphthalene, 2-methoxynaphthalene,1-methylnaphthalene, 2-methylnaphthalene, 2-methylanthracene,2-t-butylanthracene, 2-carboxyanthracene, 2-ethoxycarbonylanthracene,2-cyanoanthracene, 2-nitroanthracene, and 2-methylpentalene. To each ofthe benzene rings, a non-aromatic carbon ring, an aromatic heterocyclicring, or a non-aromatic heterocyclic ring may be condensed.

The straight-chain alkanes (A9) include, but are not limited to,methane, ethane, propane, butane, pentane, hexane, heptane, octane,nonane, decane, dodecane, tetradecane, hexadecane, and otherstraight-chain alkanes each having from about 1 to about 30 carbon atomsand preferably from about 1 to about 20 carbon atoms.

The olefins (A10) may be any of α-olefins and internal olefins each ofwhich may have a substituent (e.g., the aforementioned substituents suchas hydroxyl group and acyloxy groups) and also include dienes and otherolefins each having plural carbon-carbon double bonds. Examples of theolefins (A10) include ethylene, propylene, 1-butene, 2-butene,isobutene, 1-pentene, 2-pentene, 2,4,4-trimethyl-2-pentene, 1-hexene,2-hexene, 2,3-dimethyl-2-butene, 3-hexene, 3-hexen-1-ol, 2-hexen-1-ol,1-octen-3-ol, 1-heptene, 1-octene, 2-octene, 3-octene, 4-octene,1-nonene, 2-nonene, 1-decene, 1-undecene, 1-dodecene, 1-hexadecene,1-octadecene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene,1-acetoxy-3,7-dimethyl-2,6-octadiene, styrene, vinyltoluene,α-methylstyrene, 3-vinylpyridine, 3-vinylthiophene, and other chainolefins; cyclopropene, cyclobutene, cyclopentene, cyclohexene,cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene,cyclododecene, 1,4-cyclohexadiene, 1,4-cycloheptadiene, cyclodecadienes,cyclododecadienes, limonene, 1-p-menthene, 3-p-menthene, carveol,bicyclo[2.2.1]hept-2-ene, bidyclo[3.2.1]oct-2-ene, α-pinene, 2-bornene,and other cyclic olefins.

Each of these compounds capable of forming a radical can be used aloneor in combination, and in the latter case, the compounds used incombination may belong to the same or different categories. For example,when two or more types of these compounds, especially two or more typesof these compounds belonging to different categories, are used in areaction with oxygen or another oxygen-atom-containing gas, one of thesubstrates acts as a co-reacting agent (e.g., co-oxidizing agent) withrespect to the other and thereby yields significantly increased reactionrate in some cases.

[Radical Scavenging Compounds (B)]

The radical scavenging compounds (B) may be any compounds as long asthey can form a stable compound as a result of the reaction with aradical. Examples of such compounds include (B1) unsaturated compounds,(B2) compounds each having a methine carbon atom, (B3)heteroatom-containing compounds, and (B4) oxygen-atom-containingreactants (e.g., oxygen-atom-containing gases). Each of these compoundsmay be used alone or in combination.

These compounds may have various substituents within a range notadversely affecting the reaction. Such substituents include, but are notlimited to, halogen atoms, hydroxyl group, mercapto group, oxo group,substituted oxy groups (e.g., alkoxy groups, aryloxy groups, and acyloxygroups), substituted thio groups, carboxyl group, substitutedoxycarbonyl groups, substituted or unsubstituted carbamoyl groups, cyanogroup, nitro group, substituted or unsubstituted amino groups, sulfogroup, alkyl groups, alkenyl group, alkynyl groups, alicyclichydrocarbon groups, aromatic hydrocarbon groups, and heterocyclicgroups.

The unsaturated compounds (B1) include a wide variety of compounds eachhaving an unsaturated bond. Such compounds include, for example, (B1-1)unsaturated compounds each having an electron attractive group at theadjacent position to a carbon-carbon unsaturated bond [active olefins(electron-deficient olefins) and other active unsaturated compounds],(B1-2) compounds each having a carbon-carbon triple bond, (B1-3)compounds each having an aromatic ring, (B1-4) ketenes, (B1-5)isocyanate or thioisocyanate compounds, and (B1-6) inert olefins.

The active unsaturated compounds (B1-1) include, but are not limited to,methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate,phenyl (meth)acrylate, methyl crotonate, ethyl crotonate, methyl3-methyl-2-butenoate, ethyl 3-methyl-2-butenoate, methyl 2-pentenoate,ethyl 2-pentenoate, methyl 2-octenoate, ethyl 2-octenoate, methylcinnamate, ethyl cinnamate, methyl 4,4,4-trifluoro-2-butenoate, ethyl4,4,4-trifluoro-2-butenoate, dimethyl maleate, diethyl maleate, dimethylfumarate, diethyl fumarate, methyl 3-cyanoacrylate, ethyl3-cyanoacrylate, and other α,β-unsaturated esters; vinyl methyl ketone,vinyl ethyl ketone, methyl 1-propenyl ketone, and other α,β-unsaturatedketones; propenal, crotonaldehyde, and other α,β-unsaturated aldehydes;acrylonitrile, methacrylonitrile, and other α,β-unsaturated nitriles;(meth)acrylic acid, crotonic acid, and other α,β-unsaturated carboxylicacids; (meth)acrylamide, and other α,β-unsaturated carboxylic acidamides; N-(2-propenylidene)methylamine, N-(2-butenylidene)methylamine,and other α,β-unsaturated imines; styrene, vinyltoluene,α-methylstyrene, β-methylstyrene, and other styrene derivatives, andother compounds each having an aryl group bonded at the adjacentposition to a carbon-carbon unsaturated bond; butadiene, isoprene,2-chlorobutadiene, 2-ethylbutadiene, vinylacetylene, cyclopentadienederivatives, and other conjugated dienes (including compounds in which adouble bond and a triple bond are conjugated).

The compounds (B1-2) each having a carbon-carbon triple bond include,for example, methylacetylene and 1-butyne. The compounds (B1-3) eachhaving an aromatic ring include, for example, compounds each having abenzene ring, a naphthalene ring, or another aromatic carbon ring; andcompounds each having a pyrrole ring, a furan ring, a thiophene ring, oranother aromatic heterocyclic ring. The ketenes (B1-4) include, forexample, ketene and 2-methylketene. The isocyanate or thioisocyanatecompounds (B1-5) include, but are not limited to, methyl isocyanate,ethyl isocyanate, phenyl isocyanate, methyl thioisocyanate, ethylthioisocyanate and phenyl thioisocyanate.

The inert olefins (B1-6) may be whichever of α-olefins and internalolefins and also include dienes and other olefins each having pluralcarbon-carbon double bonds. Examples of the inert olefins (B1-6) includeethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene,2-pentene, 1-hexene, 2-hexene, 3-hexene, 1-heptene, 1-octene, 2-octene,3-octene, 4-octene, 1-nonene, 1-decene, 1-dodecene, 1,5-hexadiene,1,6-heptadiene, 1,7-octadiene, and other chain olefins (alkenes);cyclopentene, cyclohexene, cyclooctene, cyclodecene, cyclododecene, andother cyclic olefins (cycloalkenes).

The compounds (B2) each having a methine carbon atom include, forexample, the compounds exemplified as the compounds (A3). The one andsame compound can be used as the compound (A3) and the compound (B2) inthe reaction.

The heteroatom-containing compounds (B3) include, for example, (B3-1)compounds each having a sulfur atom, (B3-2) compounds each having anitrogen atom, (B3-3) compounds each having a phosphorus atom, and(B3-4) compounds each having an oxygen atom. The compounds (B3-1) eachhaving a sulfur atom include, for example, sulfides and thiols. Thecompounds (B3-2) each having a nitrogen atom include, for example,amines. The compounds (B3-3) each having a phosphorus atom include, forexample, phosphites. The compounds (B3-4) each having an oxygen atominclude, for example, N-oxides.

The oxygen-atom-containing reactants (reacting agents) (B4) include, forexample, oxygen-atom-containing gases, nitric acid, nitrous acid orsalts thereof (hereinafter referred to as “nitric acids”). Theoxygen-atom-containing gases include those each having a boiling point(or sublimation point) of less than or equal to 45° C. Suchoxygen-atom-containing gases include, but are not limited to, (B4-1)oxygen, (B4-2) carbon monoxide, (B4-3) nitrogen oxides, and (B4-4)sulfur oxides. Each of these oxygen-atom-containing reactants can beused alone or in combination.

The oxygen (B4-1) may be any of molecular oxygen and active oxygen. Themolecular oxygen is not specifically limited and includes pure oxygen,oxygen diluted with an inert gas such as nitrogen, helium, argon orcarbon dioxide, and air. Molecular oxygen is often used as the oxygen.

The carbon monoxide (B4-2) may be pure carbon monoxide or carbonmonoxide diluted with an inert gas. When carbon monoxide is used incombination with oxygen, a carboxylic acid can be obtained in a highyield as a result of the reaction with the compound (A).

The nitrogen oxides (B4-3) include compounds represented by the formula:N_(x)O_(y), wherein x is 1 or 2; and y is an integer of from 1 to 6. Inthese compounds, y is generally an integer of from 1 to 3 when x is 1;and y is generally an integer of from 1 to 6 when x is 2.

Typical examples of the nitrogen oxides are N₂O, NO, N₂O₃, NO₂, N₂O₄,N₂O₅, NO₃, and N₂O₆. Each of these nitrogen oxides can be used alone orin combination. The nitrogen oxides may be pure substances or mixturesmainly containing nitrogen oxides. Such mixtures mainly containingnitrogen oxides include, exhausted gases formed in oxidation processeswith nitric acid.

Preferred nitrogen oxides include, for example, NO, N₂O₃, NO₂ and N₂O₅.In this connection, N₂O₃ can easily be obtained upon a reaction ofdinitrogen monoxide (N₂O) and/or nitrogen monoxide (NO) with oxygen.More specifically, N₂O₃ can be prepared by introducing dinitrogenmonoxide (or nitrogen monoxide) to react and oxygen into a cooledreactor to yield a blue liquid N₂O₃. Accordingly, the reaction accordingto the present invention can be performed by introducing dinitrogenmonoxide (N₂O) and/or nitrogen monoxide (NO) and oxygen into a reactionsystem without the previous formation of N₂O₃. The nitrogen oxides canbe used in combination with oxygen. For example, by using NO₂ incombination with oxygen, the yield of the product (e.g., a nitrocompound) can further be improved.

The sulfur oxides (B4-4) include compounds represented by formula:S_(p)O_(q), wherein p is 1 or 2; and q is an integer of from 1 to 7. Inthese compounds, q is generally an integer of from 1 to 4 when p is 1;and q is generally 3 or 7 when p is 2.

Such sulfur oxides include, but are not limited to, SO, S₂O₃, SO₂, SO₃,S₂O₇ and SO₄. Each of these sulfur oxides can be used alone or incombination. As the sulfur trioxide, fuming sulfuric acid containingsulfur trioxide can be employed.

Preferred sulfur oxides include those mainly containing at least one ofsulfur dioxide (SO₂) and sulfur trioxide (SO₃). The sulfur oxide can beused in combination with oxygen. For example, by using sulfur dioxide(SO₂) in combination with oxygen, a corresponding sulfonic acid can beobtained in a high yield as a result of the reaction with the compound(A).

The salts of nitric acid or nitrous acid include, but are not limitedto, sodium salts, potassium salts, and other alkali metal salts;magnesium salts, calcium salts, barium salts, and other alkaline earthmetal salts; silver salts, aluminium salts, zinc salts, and salts ofother metals. Preferred salts include alkali metal salts of nitric acidor nitrous acid.

The nitric acids can be supplied as intact to the reaction system or maybe supplied in the form of solutions such as aqueous solutions.Alternatively, these components may be formed in the reaction system andmay be subjected to the reaction.

The reaction between the compound (A) capable of forming a radical andthe radical scavenging compound (B) is performed in the presence of, orin the absence of, a solvent. Such solvents include, but are not limitedto, acetic acid, propionic acid, and other organic acids; acetonitrile,propionitrile, benzonitrile, and other nitrites; formamide, acetamide,dimethylformamide (DMF), dimethylacetamide, and other amides; hexane,octane, and other aliphatic hydrocarbons; chloroform, dichloromethane,dichloroethane, carbon tetrachloride, chlorobenzene,trifluoromethylbenzene, and other halogenated hydrocarbons;nitrobenzene, nitromethane, nitroethane, and other nitro compounds;ethyl acetate, butyl acetate, and other esters; and mixtures of thesesolvents. In may cases, acetic acid and other organic acids,acetonitrile, benzonitrile, and other nitrites, trifluoromethylbenzene,and other halogenated hydrocarbons, ethyl acetate and other esters areused as the solvent.

The ratio of the compound (A) capable of forming a radical to theradical scavenging compound (B) can appropriately selected depending onthe types (cost, reactivity) of the two compounds or combinationsthereof. For example, the compound (A) may be used in excess (e.g., fromabout 2 to about 50 times by mole) to the compound (B). Alternatively,the compound (B) may be used in excess to the compound (A).

The process of the present invention has a feature in that the reactionsmoothly proceeds under mild conditions. A reaction temperature canappropriately be selected depending on the types of the compound (A) andcompound (B) or the type of the target product, and is, for example,from about 0° C. to about 300° C., and preferably about 20° C. to 200°C. The reaction can be performed at atmospheric pressure or under apressure (under a load). When the reaction is performed under apressure, the pressure is usually from about 0.1 to about 10 MPa (e.g.,from about 0.15 to about 8 MPa, and particularly from about 1 to about 8MPa). A reaction time can appropriately be selected within a range of,for example, from about 10 minutes to about 48 hours depending on thereaction temperature and pressure.

The reaction can be performed in a batch system, semi-batch system,continuous system or another conventional system. By adding the imidecatalyst to the reaction system in installments, the target compound canbe obtained with a higher conversion or selectivity in many cases.

After the completion of the reaction, reaction products can be separatedand purified by a technique such as filtration, concentration,distillation, extraction, crystallization, recrystallization, columnchromatography, and other separation means, or any combination of theseseparation means.

The process of the present invention yields an addition or substitutionreaction product or a derivative thereof depending on the combination ofthe compound (A) capable of forming a radical and the radical scavengingcompound (B). Such addition or substitution reaction products include,for example, carbon-carbon bonded products (e.g., coupling reactionproducts), oxidation products, carboxylation products, nitrationproducts, and sulfonation products.

For example, when the heteroatom-containing compound (A1) having acarbon-hydrogen bond at the adjacent position to the heteroatom is usedas the compound (A), the adjacent position to the heteroatom is combinedwith an atom (e.g., a carbon atom) constituting an unsaturated bond ofthe unsaturated compound (B1), to the methine carbon atom of thecompound (B2) having a methine carbon atom, or to the heteroatom of theheteroatom-containing compound (B3), and thereby yields an addition orsubstitution reaction product or a derivative thereof.

When the compound (A2) having a carbon-heteroatom double bond (e.g., thecarbonyl-group-containing compound) is employed as the compound (A), abond between a carbon atom relating to the carbon-heteroatom double bond(e.g., a carbonyl carbon atom) and an atom adjacent to the carbon atomis broken, and an atomic group containing the carbon-heteroatom doublebond (e.g., an acyl group) is combined with the aforementioned positionof the compound (B1), (B2) or (B3) to yield an addition or substitutionreaction product or a derivative thereof.

When the compound (A3) having a methine carbon atom is used as thecompound (A) capable of forming a radical, the methine carbon atom iscombined with the aforementioned position of the compound (B1), (B2) or(B3) to yield an addition or substitution reaction product or aderivative thereof.

Generally, the use of the unsaturated compound (B1) as the radicalscavenging compound (B) yields an addition reaction product, and the useof the compound (B2) having a methine carbon atom as the compound (B)yields a substitution reaction product (e.g., a coupling product).

The reaction between the oxygen-atom-containing reactant (B4) as theradical scavenging compound (B) with the compound (A) capable of forminga radical yields an organic compound having an oxygen-atom-containinggroup (e.g., hydroxyl group, oxo group, carboxyl group, nitro group, orsulfur acid group) depending on the type of the oxygen-atom-containingreactant.

According to the process of the present invention, a complicated organiccompound can be obtained through one step by using two or more types ofthe compounds (A) capable of forming a radical and/or the radicalscavenging compounds (B) to thereby invite sequential addition orsubstitution reactions. For example, when the unsaturated compound (B1)and oxygen (B4-1) as the radical scavenging compounds (B) are allowed toreact with the compound (A), a group derived from the compound (A) iscombined with one of the two carbon atoms constituting the unsaturatedbond as mentioned above, and a hydroxyl group derived from the oxygen isintroduced into the other carbon atom.

A reaction mechanism in the process of the present invention is notclarified in detail, but is supposed as follows. During the reaction, anoxidized active species [e.g., imido-N-oxy radical (>NO•)] is formed,the oxidized active species withdraws a hydrogen from the compound (A)and allows the compound (A) to forma radical, for example, at the carbonatom at the adjacent position to the heteroatom in the compound (A1), atthe carbon atom relating to the carbon-heteroatom double bond in thecompound (A2), at the methine carbon atom in the compound (A3), or atthe carbon atom at the adjacent position to the unsaturated bond in thecompound (A4); the thus-formed radical reacts with the compound (B) andthereby yields a corresponding addition or substitution reactionproduct.

The above-formed addition or substitution reaction product may furtherundergo, for example, dehydration reaction, cyclization reaction,decarboxylation reaction, rearrangement reaction, or isomerizationreaction in the reaction system depending on the structure thereof orreaction conditions, and thereby yields a corresponding derivative.

The reaction between the compound (A) capable of forming a radical andthe radical scavenging compound (B) should preferably be performed underconditions with minimal polymerization inhibitors (e.g., hydroquinone).For example, the proportion of the polymerization inhibitor in thereaction system should preferably be less than or equal to 1000 ppm, andmore preferably less than or equal to 100 ppm. If the proportion of thepolymerization inhibitor exceeds 1000 ppm, a reaction rate is liable todecrease, and the imide catalyst and/or the co-catalyst has to be usedin large amounts in some cases. In contrast, when the proportion of thepolymerization inhibitor in the reaction system is low, the reactionrate increases to increase a yield, and the reaction results have a highreproducibility to stably yield a target compound. The unsaturatedcompounds (B1) or other compounds for use in commercial, to which apolymerization inhibitor is added, should preferably be subjected toelimination of the polymerization inhibitor by, for example,distillation, prior to the reaction. The same goes for any reaction inwhich the compound (A) is allowed to react with the compound (B) in thepresence of the imide compound.

By using an appropriate combination of the compound (A) capable offorming a radical and the radical scavenging compound (B) in thereaction according to the present invention, various organic compoundsas mentioned below can be obtained.

1. Production of 1,3-Dihydroxy Compounds

A first embodiment of such production will be described below. Bycatalysis of the imide compound, an alcohol represented by followingFormula (2):

wherein R^(a) and R^(b) are the same or different and are each ahydrogen atom or an organic group, where R^(a) and R^(b) may be combinedto form a ring with the adjacent carbon atom, is allowed to react with(B4-1) oxygen and (B11) an active olefin represented by followingFormula (3):

wherein R^(c), R^(d) and R^(e) are the same or different and are each ahydrogen atom or an organic group; and Y is an electron attractivegroup, where R^(c), R^(d), R^(e) and Y may be combined with each otherto form a ring with the adjacent carbon atom or carbon-carbon bond, andthereby yields a 1,3-dihydroxy compound represented by following Formula(4):

wherein R^(a), R^(b), R^(c), R^(d), R^(e) and Y have the same meaningsas defined above. This reaction can be performed pursuant to a process(a process using a catalytic 5-membered N-hydroxy cyclic imide compound)described in PCT International Publication No.

[Alcohols]

The organic group in R^(a) and R^(b) in Formula (2) has only to be anorganic group that does not adversely affect the reaction (e.g., anorganic group that is not reactive under reaction conditions accordingto the process). Such organic groups include, for example, hydrocarbongroups and heterocyclic groups.

The hydrocarbon groups include aliphatic hydrocarbon groups, alicyclichydrocarbon groups, and aromatic hydrocarbon groups. Such aliphatichydrocarbon groups include, but are not limited to, straight- orbranched-chain aliphatic hydrocarbon groups (alkyl groups, alkenylgroups, and alkynyl groups) each having from about 1 to about 20 carbonatoms. The alicyclic hydrocarbon groups include, but are not limited to,monocyclic alicyclic hydrocarbon groups (e.g., cycloalkyl groups andcycloalkenyl groups) each having from about 3 to about 20 carbon atoms(preferably having from about 3 to about 15 carbon atoms); and bridgedcyclic hydrocarbon groups. The aromatic hydrocarbon groups include, forexample, aromatic hydrocarbon groups each having from about 6 to about14 carbon atoms. These hydrocarbon groups may have various substituents.

Heterocyclic rings constituting the heterocyclic groups in R^(a) andR^(b) include aromatic heterocyclic rings and non-aromatic heterocyclicrings. Such heterocyclic rings include heterocyclic rings eachcontaining an oxygen atom as aheteroatom, heterocyclic rings eachcontaining a sulfur atom as a heteroatom, and heterocyclic rings eachcontaining a nitrogen atom as a heteroatom. These heterocyclic groupsmay have at least one substituent.

The rings formed by R^(a) and R^(b) with the adjacent carbon atominclude, but are not limited to, cyclopentane, cyclohexane, cyclohexene,cyclododecane, decalin, adamantane, and other non-aromatic carbon rings(cycloalkane rings, cycloalkene rings, and bridged carbon rings) eachhaving from about 3 to about 20 members (preferably from about 3 toabout 15 members, more preferably from about 5 to about 15 members, andtypically from about 5 to about 8 members). These rings may have atleast one substituent (e.g., similar groups to the substituents that thehydrocarbon groups may have). To each of these rings, another ring (anon-aromatic ring or an aromatic ring) may be condensed.

Preferred substituent R^(a) includes hydrogen atom, C₁–C₄ alkyl groups,and C₆–C₁₄ aryl groups. Preferred R^(b) includes hydrogen atom, C₁–C₁₀aliphatic hydrocarbon groups and alicyclic hydrocarbon groups.Alternatively, R^(a) and R^(b) are preferably combined to form anon-aromatic carbon ring having from about 3 to about 15 members(particularly from about 5 to about 8 members) with the adjacent carbonatom.

The alcohols represented by Formula (2) include, for example, thoseexemplified as the primary or secondary alcohols in compounds (A1-1).

Preferred alcohols include secondary alcohols (e.g., 2-propanol, s-butylalcohol, and other aliphatic secondary alcohols; 1-cyclohexylethanol,and other secondary alcohols each having an aliphatic hydrocarbon group(e.g., a C₁–C₄ alkyl group, or a C₆–C₁₄ aryl group) and a non-aromaticcarbocyclic group (e.g., a C₃–C₁₅ cycloalkyl group or a cycloalkenylgroup) combined with a carbon atom that is combined with a hydroxylgroup; cyclopentanol, cyclohexanol, 2-adamantanol, and other alicyclicsecondary alcohols each having from about 3 to about 15 members;1-phenylethanol, and other aromatic secondary alcohols), and alcohols inwhich the substituent R^(b) is a bridged cyclic hydrocarbon group.

[Active Olefins]

The organic groups in R^(c), R^(d) and R^(e) in the active olefinsrepresented by Formula (3) can be any organic groups, as long as they donot adversely affect the reaction (e.g., organic groups that are inertunder reaction conditions according to the process of the presentinvention). Such organic groups include, but are not limited to, halogenatoms, hydrocarbon groups, heterocyclic groups, substituted oxycarbonylgroups (e.g., alkoxycarbonyl groups, aryloxycarbonyl groups,aralkyloxycarbonyl groups, and cycloalkyloxycarbonyl groups), carboxylgroup, substituted or unsubstituted carbamoyl groups (N-substituted orunsubstituted amide groups), cyano group, nitro group, sulfur acidradicals (sulfonic acid groups, and sulfinic acid groups), sulfur acidester groups (sulfonic acid ester groups, and sulfinic acid estergroups), acyl groups, hydroxyl group, alkoxy groups, and N-substitutedor unsubstituted amino groups. The carboxyl group, hydroxyl group andamino groups may be protected by a conventional protecting group.

The halogen atoms include fluorine, chlorine, bromine, and iodine atoms.The hydrocarbon groups include, for example, the groups exemplified asthe hydrocarbon groups in R^(a) and R^(b). These hydrocarbon groups mayhave at least one substituent. The heterocyclic groups include, forexample, the groups exemplified as the heterocyclic groups in R^(a) andR^(b). These heterocyclic groups may have at least one substituent. Thealkoxycarbonyl groups include, but are not limited to, methoxycarbonyl,ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl,t-butoxycarbonyl, and other C₁–C₆ alkoxy-carbonyl groups. Thearyloxycarbonyl groups include, but are not limited to,phenyloxycarbonyl group. The aralkyloxycarbonyl groups include, forexample, benzyloxycarbonyl group. Illustrative cycloalkyloxycarbonylgroups are cyclopentyloxycarbonyl and cyclohexyloxycarbonyl groups.

The substituted carbamoyl groups include, for example,N-methylcarbamoyl, and N,N-dimethylcarbamoyl groups. Illustrativesulfonic acid ester groups are methyl sulfonate, ethyl sulfonate, andother sulfonic acid C₁–C₄ alkyl ester groups. Illustrative sulfinic acidester groups are methyl sulfinate, ethyl sulfinate, and other sulfinicacid C₁–C₄ alkyl ester groups. The acyl groups include, but are notlimited to, acetyl, propionyl, and other aliphatic acyl groups (e.g.,C₂–C₇ aliphatic acyl groups), and benzoyl, and other aromatic acylgroups. The alkoxy groups include, but are not limited to, methoxy,ethoxy, propoxy, butoxy, and other alkoxy groups each having from about1 to about 6 carbon atoms. The N-substituted amino groups include, forexample, N,N-dimethylamino, N,N-diethylamino, and piperidino groups.

Preferred R^(c), R^(d), and R^(e) include, for example, hydrogen atom,hydrocarbon groups [e.g., C₁–C₆ aliphatic hydrocarbon groups(particularly C₁–C₄ aliphatic hydrocarbon groups), C₆–C₁₄ aryl groups(e.g., phenyl group), cycloalkyl groups (e.g., cycloalkyl groups eachhaving from about 3 to about 8 members), haloalkyl groups (e.g.,trifluoromethyl group, and other C₁–C₆ haloalkyl group, particularlyC₁–C₄ haloalkyl groups)], heterocyclic groups, substituted oxycarbonylgroups (e.g., C₁–C₆ alkoxy-carbonyl groups, aryloxycarbonyl groups,aralkyloxycarbonyl groups, and cycloalkyloxycarbonyl groups), carboxylgroup, substituted or unsubstituted carbamoyl groups, cyano group, nitrogroup, sulfur acid groups, sulfur acid ester groups, and acyl groups.Typically preferred R^(c) and R^(d) are, for example, hydrogen atom,C₁–C₆ aliphatic hydrocarbon groups (particularly C₁–C₄ aliphatichydrocarbon groups), C₆–C₁₄ aryl groups (e.g., phenyl group), cycloalkylgroups (e.g., cycloalkyl groups each having from about 3 to about 8members), haloalkyl groups (e.g., trifluoromethyl group and other C₁–C₆haloalkyl groups, particularly C₁–C₄ haloalkyl groups)], substitutedoxycarbonyl groups (e.g., C₁–C₆ alkoxy-carbonyl groups, aryloxycarbonylgroups, aralkyloxycarbonyl groups, and cycloalkyloxycarbonyl groups),and cyano group. Typically preferred R^(e) includes, for example,hydrogen atom, and C₁–C₆ aliphatic hydrocarbon groups (especially, C₁–C₄aliphatic hydrocarbon groups).

The rings formed by R^(c), R^(d) and R^(e) (R^(c) and R^(d), R^(c) andR^(e), R^(d) and R^(e), or R^(c) and R^(d) and R^(e)) together with theadjacent carbon atom or carbon-carbon bond include cyclopropane,cyclobutane, cyclopentane, cyclopentene, cyclohexane, cyclohexene,cyclooctane, cyclododecane, and other alicyclic carbon rings (e.g.,cycloalkane rings and cycloalkene rings) each having from about 3 toabout 20 members. These rings may have at least one substituent, andanother ring (a non-aromatic ring or an aromatic ring) may be condensedto each of these rings.

The electron attractive groups Y include, but are not limited to,methoxycarbonyl, ethoxycarbonyl, and other alkoxycarbonyl groups;phenoxycarbonyl, and other aryloxycarbonyl groups; formyl, acetyl,propionyl, benzoyl, and other acyl groups; cyano group; carboxyl group;carbamoyl, N,N-dimethylcarbamoyl, and other substituted or unsubstitutedcarbamoyl groups; —CH═N—R, where R is, for example, an alkyl group;phenyl, naphthyl, and other aryl groups; vinyl, 1-propenyl, ethynyl, andother 1-alkenyl groups or 1-alkynyl groups.

The rings formed by Y and at least one of R^(c), R^(d), and R^(e) withthe adjacent carbon atom or carbon-carbon bond include, but are notlimited to, cyclopentadiene ring, pyrrole ring, furan ring, andthiophene ring.

Typical active olefins represented by Formula (3) include the compoundsexemplified as the active unsaturated compounds (B1-1).

[Reaction]

The reaction of the alcohol represented by Formula (2) with the activeolefin represented by Formula (3) and oxygen can be performed inaccordance with the procedure described in the reaction between thecompound (A) and the compound (B).

In this reaction, the 1,3-dihydroxy compound represented by Formula (4)is supposed to be formed in the following manner. A1-hydroxyalkylradical corresponding to the alcohol represented by Formula (2) isformed in the system, attacks and is added to a carbon atom at thebeta-position of the group Y between the two carbon atoms constitutingan unsaturated bond of the active olefin represented by Formula (3), andoxygen attacks a radical at the alpha-position formed as a result of theaddition and thereby yields the 1,3-dihydroxy compound represented byFormula (4).

In the compound represented by Formula (4) formed as a result of thereaction, when Y is a carboxyl group or an ester group such asalkoxycarbonyl group or aryl oxycarbonyl group, a cyclization reactionmay further proceed in the system to yield a furanone derivative(α-hydroxy-γ-butyrolactone derivative) represented by Formula (6), asdescribed later. The yield of the furanone derivative can be improved bycontrolling the type and proportion of the co-catalyst or furthersubjecting the product to aging after the addition reaction (or furtheroxidation reaction). A reaction temperature in the aging period may beset higher than that in the addition reaction. The furanone derivativecan also be produced by isolating the compound represented by Formula(4), for example dissolving the isolated compound in a solvent, andheating the solution according to necessity. Such solvents include, butare not limited to, the solvents mentioned later, as well as benzene,toluene, and other aromatic hydrocarbons; cyclohexane and otheralicyclic hydrocarbons; acetone, cyclohexanone, and other ketones;diethyl ether, tetrahydrofuran, and other ethers; methanol, ethanol,isopropyl alcohol, and other alcohols. A reaction temperature in thisprocedure is, for example, from about 0° C. to about 150° C., andpreferably from about 30° C. to about 100° C.

2. Production of α-Hydroxy-γ-butyrolactone Derivatives

By catalysis of the imide compound, the alcohol represented by Formula(2) is allowed to react with (B4-1) oxygen and an α,β-unsaturatedcarboxylic acid derivative represented by following Formula (5):

wherein R^(c), R^(d), R^(e) and R^(f) are the same or different and areeach a hydrogen atom or an organic group, where R^(c), R^(d) and R^(e)may be combined with each other to form a ring with the adjacent carbonatom or carbon-carbon bond, and thereby yields anα-hydroxy-γ-butyrolactone derivative represented by following Formula(6):

wherein R^(a), R^(b), R^(c), R^(d) and R^(e) have the same meanings asdefined above. This reaction can be performed pursuant to the process (aprocess using a catalytic 5-membered N-hydroxy cyclic imide compound)described in PCT International Publication No. WO00/35835.

[Alcohols]

The alcohols represented by Formula (2) include similar alcohols tothose in the production of the 1,3-dihydroxy compounds.

[α,β-Unsaturated Carboxylic Acid Derivatives]

The substituents R^(c), R^(d) and R^(e) in Formula (5) are similar toR^(c), R^(d) and R^(e) in Formula (3). Organic groups in R^(f) includeorganic groups that do not adversely affect the reaction (e.g., organicgroups that are inert under reaction conditions according to the processof the present invention) such as hydrocarbon groups and heterocyclicgroups. If the compound represented by Formula (5) has a substitutedoxycarbonyl group in addition to —CO₂R^(f) group indicated in Formula(5), the —CO₂R^(f) group is involved in a cyclization reaction, but theother substituted oxycarbonyl group can remain as intact in the product.The other substituted oxycarbonyl group is therefore included in theinert organic groups.

When at least one of R^(c) and R^(d) is an electron attractive organicgroup, a target α-hydroxy-γ-butyrolactone derivative can be obtained ina significantly high yield. Such electron attractive organic groupsinclude, for example, haloalkyl groups, substituted oxycarbonyl groups,carboxyl group, substituted or unsubstituted carbamoyl groups, cyanogroup, nitro group, sulfur acid groups, and sulfur acid ester groups.

The substituent R^(f) is often a hydrogen atom or a hydrocarbon group,and is preferably a C₁–C₆ alkyl group (especially a C₁–C₄ alkyl group),a C₂–C₆ alkenyl group (especially a C₂–C₄ alkenyl group), or a C₆–C₁₀aryl group.

Typical examples of the α,β-unsaturated carboxylic acid derivativesrepresented by Formula (5) are (meth)acrylic acid; methyl(meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, phenyl(meth)acrylate, and other (meth)acrylic esters; crotonic acid; methylcrotonate, ethyl crotonate, and other crotonic esters;3-methyl-2-butenoic acid; methyl 3-methyl-2-butenoate, ethyl3-methyl-2-butenoate, and other 3-methyl-2-butenoic esters; 2-pentenoicacid; methyl 2-pentenoate, ethyl 2-pentenoate, and other 2-pentenoicesters; 2-octenoic acid; methyl 2-octenoate, ethyl 2-octenoate, andother 2-octenoic esters; cinnamic acid; methyl cinnamate, ethylcinnamate, and other cinnamic esters; 4,4,4-trifluoro-2-butenoic acid;methyl 4,4,4-trifluoro-2-butenoate, ethyl 4,4,4-trifluoro-2-butenoate,and other 4,4,4-trifluoro-2-butenoic esters; maleic acid; dimethylmaleate, diethylmaleate, and other maleic esters; fumaric acid; dimethylfumarate, diethyl fumarate, and other fumaric esters; 3-cyanoacrylicacid; methyl 3-cyanoacrylate, ethyl 3-cyanoacrylate, and other3-cyanoacrylic esters, and other α,β-unsaturated carboxylic acids eachhaving from about 2 to about 15 carbon atoms or esters thereof (e.g.,C₁–C₆ alkyl esters, C₂–C₆ alkenyl esters, and aryl esters).

[Reaction]

The reaction of the alcohol represented by Formula (2) with oxygen andthe α,β-unsaturated carboxylic acid derivative represented by Formula(5) can be performed pursuant to the process described in the reactionbetween the compound (A) and the compound (B).

According to the process of the present invention, anα,γ-dihydroxycarboxylic acid derivative (a kind of the compoundsrepresented by Formula (4)) represented by following Formula (7) isformed as a reaction intermediate:

wherein R^(a), R^(b), R^(c), R^(d), R^(e), and R^(f) have the samemeanings as defined above. This compound is supposed to be formed in thefollowing manner. A 1-hydroxyalkyl radical corresponding to the alcoholrepresented by Formula (2) is formed in the system, attacks and is addedto the beta-position of the α,β-unsaturated carboxylic acid derivativerepresented by Formula (5), and oxygen attacks a radical at thealpha-position formed as a result of the addition to yield the compoundin question. The formed α,β-dihydroxycarboxylic acid derivativerepresented by Formula (7) undergoes cyclization under reactionconditions and thereby yields the target α-hydroxy-γ-butyrolactonederivative represented by Formula (6).

When a primary alcohol is used as the alcohol represented by Formula (2)(i.e., when R^(a) is a hydrogen atom), a β-acyl-α-hydroxycarboxylic acidderivative of following Formula (8) may be formed in addition to thecompound represented by Formula (6). This is provably because an acylradical [R^(b)C(═O)•] is formed in the system:

wherein R^(b), R^(c), R^(d), R^(e), and R^(f) have the same meanings asdefined above. The α-hydroxy-γ-butyrolactone derivative can also beprepared by isolating the α,γ-dihydroxycarboxylic acid derivativerepresented by Formula (7), for example, dissolving the same in asolvent, and heating the solution according necessity, as mentionedabove.

3. Production of Conjugated Unsaturated Compounds

By catalysis of the imide compound, an alcohol represented by followingFormula (2a):

wherein R^(i) and R^(j) are the same or different and are each ahydrogen atom or an organic group, where R^(i) and R^(j) may be combinedto form a ring with the adjacent carbon atom, is allowed to react withoxygen and an active olefin represented by following Formula (3a):

wherein R^(d) and R^(e) are the same or different and are each ahydrogen atom or an organic group; and Y is an electron attractivegroup, where R^(d), R^(e) and Y may be combined with each other to forma ring with the adjacent carbon atom or carbon-carbon bond, and therebyyields a conjugated unsaturated compound represented by followingFormula (9):

wherein R^(d), R^(e), R^(i), R^(j) and Y have the same meanings asdefined above. This reaction can be performed pursuant to a process (aprocess using a catalytic 5-membered N-hydroxy cyclic imide compound)described in PCT International Publication No. WO00/35835.

Organic groups in R^(i) and R^(j) in Formula (2a) are the same as theorganic groups in R^(a) and R^(b). Rings which are formed by R^(i) andR^(j) with the adjacent carbon atom include similar rings to thoseformed by R^(a) and R^(b) with the adjacent carbon atom.

Preferred substituent R^(i) includes, for example, hydrogen atom, C₁–C₄alkyl groups, and C₆–C₁₄ aryl groups. Preferred R^(j) includes, forexample, hydrogen atom, C₁–C₁₀ aliphatic hydrocarbon groups (especiallyC₁–C₁₀ alkyl groups), and alicyclic hydrocarbon groups (e.g., C₃–C₁₅cycloalkyl groups or cycloalkenyl groups; and bridged cyclic hydrocarbongroups). Alternatively, R^(i) and R^(j) are preferably combined to forma non-aromatic carbon ring having from about 3 to about 15 members(particularly from about 5 to about 8 members) with the adjacent carbonatom.

The alcohols represented by Formula (2a) include a wide variety ofprimary alcohols. Typical examples of such alcohols are ethanol,1-propanol, 1-butanol, 2-methyl-1-propanol, 1-pentanol, 1-hexanol, andother saturated or unsaturated aliphatic primary alcohols each havingfrom about 2 to about 30 (preferably from about 2 to about 20, and morepreferably from about 2 to about 15) carbon atoms; cyclopentylmethylalcohol, cyclohexylmethyl alcohol, and other saturated or unsaturatedalicyclic primary alcohols; 2-phenylethyl alcohol, 3-phenylpropylalcohol, cinnamic alcohol, and other aromatic primary alcohols; and2-(2-hydroxyethyl)pyridine, and other heterocyclic alcohols.

The compounds represented by Formula (3a) correspond to compoundsrepresented by Formula (3) where R^(c) is a hydrogen atom. Thesubstituents R^(d), R^(e), and Y in Formula (3a) are similar to those inFormula (3).

A reaction can be performed pursuant to the process for producing the1,3-dihydroxy compound. In this reaction, a compound corresponding toFormula (4) (a compound of Formula (4) where Ra═R^(i)R^(j)CH group andR^(b)═R^(c)═H) can be formed in addition to the conjugated unsaturatedcompound represented by Formula (9). When a compound represented byFormula (3a), where Y is a CO₂R^(f) group, is used as the compound ofFormula (3a), a compound corresponding to Formula (6) (a compound ofFormula (6) where R^(a)═R^(i)R^(j)CH group and R^(b)═R^(c)═H) can beformed in addition to the conjugated unsaturated compound represented byFormula (9).

For example, when n-propyl alcohol is allowed to react with ethylacrylate, ethyl 2,4-dihydroxyhexanoate corresponding to Formula (4) and4-ethyl-2-hydroxy-γ-butyrolactone corresponding to Formula (6) areformed under some conditions in addition to the target ethyl sorbate.

The conjugated unsaturated compound represented by Formula (9) issupposed to be formed in the following manner. Initially, a dihydroxycompound corresponding to Formula (4) [a compound of Formula (4) whereR^(a)═R^(i)R^(j)CH group, and R^(b)═R^(c)═H] is formed, two molecules ofwater are then eliminated from this compound and thereby yields thecompound in question. Reaction products can be separated and purified inthe same separation means as above.

4. Production of β-Hydroxyacetal Compounds

By catalysis of the imide compound, an acetal represented by followingFormula (10):

wherein R^(k), R^(m), R^(n) are the same or different and are each ahydrogen atom or an organic group, where R^(m) and R^(n) may be combinedto form a ring with the adjacent two oxygen atoms and the carbon atomindicated in the formula, is allowed to react with oxygen and the activeolefin represented by Formula (3) and thereby yields a β-hydroxyacetalcompound represented by following Formula (11):

wherein R^(c), R^(d), R^(e), R^(k), R^(m), R^(n), and Y have the samemeanings as defined above. This reaction can be performed pursuant to aprocess (a process using a catalytic 5-membered N-hydroxy cyclic imidecompound) described in PCT International Publication No. WO00/35835.

In Formula (10), organic groups in R^(k), R^(m) and R^(n) includeorganic groups similar to those in R^(a) and R^(b). Rings formed byR^(m) and R^(n) with the adjacent two oxygen atoms and carbon atominclude, for example, 1,3-dioxolane ring and 1,3-dioxane ring. To theserings, substituents such as alkyl groups and halogen atoms can bebonded.

Preferred substituent R^(k) includes, for example, hydrogen atom; C₁–C₁₀aliphatic hydrocarbon groups (especially, C₁–C₄ alkyl groups); alicyclichydrocarbon groups (cycloalkyl groups, cycloalkenyl groups, and bridgedcyclic hydrocarbon groups) each having from about 3 to about 15 carbonatoms; and C₆–C₁₄ aryl groups. Preferred R^(m) and R^(n) include, forexample, hydrogen atom; C₁–C₆ aliphatic hydrocarbon groups(particularly, C₁–C₄ alkyl groups); and alicyclic hydrocarbon groupseach having from about 3 to about 10 carbon atoms. Alternatively, R^(m)and R^(n) are preferably combined to form a ring with the adjacent twooxygen atoms and carbon atom.

The acetals represented by Formula (10) include compounds exemplified asthe acetals each having a carbon-hydrogen bond at the adjacent positionto an oxygen atom in the compounds (A1-3). Typical examples of suchacetals include 1,3-dioxolane, 2-methyl-1,3-dioxolane,2-ethyl-1,3-dioxolane, and other 1,3-dioxolane compounds;2-methyl-1,3-dioxane, and other 1,3-dioxane compounds; and acetaldehydedimethyl acetal, and other dialkyl acetals.

The active olefin represented by Formula (3) is the same as statedabove. A reaction can be performed according to the process of thepresent invention for producing an organic compound. Reaction productscan be separated and purified in a similar separation means to thosementioned above.

In this reaction, the β-hydroxyacetal compound represented by Formula(11) is supposed to be formed in the following manner. Initially, a1,1-di-substituted oxyalkyl radial corresponding to the acetalrepresented by Formula (10) is formed, this radical attacks and is addedto a carbon atom at the beta-position of the group Y between the twocarbon atoms constituting an unsaturated bond of the active olefinrepresented by Formula (3), and oxygen attacks a radical at thealpha-position formed as a result of the addition and thereby yields thecompound in question.

5. Production of Hydroxy Compounds

By catalysis of the imide compound, a compound having a methine carbonatom and represented by following Formula (12):

wherein R^(o), R^(p) and R^(q) are the same or different and are each anorganic group, where R^(o), R^(p) and R^(q) may be combined with eachother to form a ring with the adjacent carbon atom, is allowed to reactwith oxygen and the active olefin represented by Formula (3) and therebyyields at least one of hydroxy compounds represented by followingFormula (13) and (14):

wherein R^(c), R^(d), R^(e), R^(o), R^(p), R^(q) and Y have the samemeanings as defined above. This reaction can be performed pursuant to aprocess (a process using a catalytic 5-membered N-hydroxy cyclic imidecompound) described in PCT International Publication No. WO00/35835.

The organic groups in R^(o), R^(p) and R^(q) in Formula (12) includeorganic groups similar to those in R^(a) and R^(b). Preferred organicgroups include, for example, C₁–C₁₀ aliphatic hydrocarbon groups(especially, C₁–C₄ alkyl groups); alicyclic hydrocarbon groups(cycloalkyl groups, cycloalkenyl groups, and bridged cyclic hydrocarbongroups) each having from about 3 to about 15 carbon atoms; and C₆–C₁₄aryl groups.

The rings formed by R^(o), R^(p) and R^(q) (R^(o) and R^(p), R^(p) andR^(q), R^(o) and R^(q), or R^(o) and R^(p) and R^(q)) together with theadjacent carbon atom include, but are not limited to, cyclopentene,cyclohexane, and other monocyclic alicyclic carbon rings (cycloalkanerings and cycloalkene rings) each having from about 3 to about 20members (preferably from about 3 to about 15 members, more preferablyfrom about 5 to about 15 members, and typically from about 5 to about 8members); adamantane ring, perhydroindene ring, decalin ring,perhydrofluorene ring, perhydroanthracene ring, perhydrophenanthrenering, tricyclo[5.2.1.0^(2,6)]decane ring, perhydroacenaphthene ring,perhydrophenalene ring, norbornane ring, norbornene ring, and otherbicyclic, tricyclic or tetracyclic bridged carbon rings. These rings mayeach have at least one substituent.

When R^(o), R^(p) and R^(q) are combined to form a bridged cyclic carbonring with the adjacent carbon atom, the methine carbon atom indicated inFormula (12) should preferably be a carbon atom at a bridgeheadposition.

The compounds represented by Formula (12) having a methine carbon atominclude, for example, compounds exemplified as the compounds (A3) eachhaving a methine carbon atom, such as the bridged cyclic compounds(A3-1a), the non-aromatic cyclic compounds (A3-1b) each having ahydrocarbon group combined with a ring, and the chain compounds (A3-2)each having a methine carbon atom.

The active olefins represented by Formula (3) are the same as mentionedabove. A reaction can be performed according to the process of thepresent invention for producing an organic compound. Reaction productscan be separated and purified in the same separation means as above.

In this reaction, the hydroxy compound represented by Formula (13) orthe hydroxy compound represented by Formula (14) is supposed to beformed in the following manner. A radical is formed at the methinecarbon position of the compound represented by Formula (12), attacks andis added to a carbon atom at the alpha-position or a carbon atom at thebeta-position of the group Y between the two carbon atoms constitutingan unsaturated bond of the active olefin represented by Formula (3), andoxygen attacks a radical at the alpha-position or beta-position formedas a result of the addition and thereby yields the hydroxy compound inquestion.

Of the hydroxy compounds represented by Formula (13) thus prepared,preferred compounds are compounds where R^(o), R^(p), and R^(q) arecombined to form a bridged cyclic carbon ring (e.g., adamantane ring)with the adjacent carbon atom, each of R^(c), R^(d), and R^(e) is ahydrogen atom or a C₁–C₄ alkyl group, Y is an alkoxycarbonyl group(e.g., a C₁–C₄ alkoxy-carbonyl group), an aryloxycarbonyl group, an acylgroup (e.g., a C₁–C₄ acyl group, or a benzoyl group) or a carboxylgroup. Such compounds are useful as, for example, materials forpharmaceuticals, agricultural chemicals, and other fine chemicals, andmaterials for functional polymers.

6. Production of Carbonyl Compounds (1)

By catalysis of the imide compound, the compound having a methine carbonatom represented by Formula (12) is allowed to react with oxygen and anactive olefin represented by following Formula (3b):

wherein R^(c) and R^(d) are the same or different and are each ahydrogen atom or an organic group; and Y is an electron attractivegroup, where R^(c), R^(d) and Y may be combined with each other to forma ring with the adjacent carbon atom or carbon-carbon bond, and therebyyields a carbonyl compound represented by following Formula (15):

wherein R^(c), R^(d), R^(o), R^(p), Rq and Y have the same meanings asdefined above. This reaction can be performed pursuant to a process (aprocess using a catalytic 5-membered N-hydroxy cyclic imide compound)described in PCT International Publication No. WO00/35835.

This process corresponds to the production of the hydroxy compound inwhich a compound having a hydrogen atom as R^(e) is employed as theactive olefin represented by Formula (3). In this case, the carbonylcompound represented by Formula (15) is formed instead of, or inaddition to, acompound corresponding to Formula (13) (R^(e)═H) and/or acompound corresponding to Formula (14) (R^(e)═H). The proportion of theformed two compounds can be controlled by appropriately selectingreaction conditions such as reaction temperature, amount of thecatalyst, and the type of the co-catalyst (metallic compound).

The carbonyl compound represented by Formula (15) is supposed to beformed by the oxidation of the compound corresponding to Formula (13)(R^(e)═H) in a system.

Of the carbonyl compounds represented by Formula (15) thus prepared,preferred compounds are compounds where R^(o), R^(p), and R^(q) arecombined to form a bridged cyclic carbon ring (e.g., adamantane ring)with the adjacent carbon atom, each of R^(c) and R^(d) is a hydrogenatom or a C₁–C₄ alkyl group, Y is an alkoxy carbonyl group (e.g., aC₁–C₄ alkoxy-carbonyl group), an aryloxycarbonyl group, an acyl group(e.g., a C₁–C₄ acyl group, or a benzoyl group) or a carboxyl group. Suchcompounds are useful as, for example, materials for pharmaceuticals,agricultural chemicals and other fine chemicals, and materials forfunctional polymers.

7. Production of Compounds Having Electron Attractive Group

By catalysis of the imide compound, the compound represented by Formula(12) having a methine carbon atom is allowed to react with oxygen and anactive olefin represented by following Formula (3c):

wherein R^(e) is a hydrogen atom or an organic group; and Y is anelectron attractive group, and thereby yields a compound having anelectron attractive group and represented by following Formula (16):

wherein R^(e), R^(o), R^(p), R^(q) and Y have the same meanings asdefined above. This reaction can be performed pursuant to a process (aprocess using a catalytic 5-membered N-hydroxy cyclic imide compound)described in PCT International Publication No. WO00/35835.

This process corresponds to the production of the hydroxy compound wherea compound having hydrogen atoms as R^(c) and R^(d) is employed as theactive olefin represented by Formula (3). In this process, the compoundrepresented by Formula (16) is formed instead of, or in addition to, acompound corresponding to Formula (13) (R^(c)═R^(d)H), a compoundcorresponding to Formula (14) (R^(c)═R^(d)═H) or a compoundcorresponding to Formula (15) (only in the case where R^(c)═R^(d)═H, andR^(e)═H). The proportions of the individual formed compounds can becontrolled by appropriately selecting reaction conditions such asreaction temperature, amount of the catalyst, and the type of theco-catalyst (metallic compound).

The compound represented by Formula (16) is supposed to be formed in thefollowing manner. The methylol group of a compound corresponding toFormula (14) (R^(c)═R^(d)═H) is further oxidized in the system to yielda carboxyl group, and the carboxyl group undergoes decarboxylation toyield the compound in question.

Of the carbonyl compounds represented by Formula (16) thus prepared,preferred compounds include compounds where R^(o), R^(p), and R^(q) arecombined to form a bridged cyclic carbon ring (e.g., adamantane ring)with the adjacent carbon atom, R^(e) is a hydrogen atom or a C₁–C₄ alkylgroup, and Y is an alkoxycarbonyl group (e.g., aC₁–C₄alkoxy-carbonylgroup), anaryloxycarbonyl group, an acyl group(e.g., a C₁–C₄ acyl group or a benzoyl group) or a carboxyl group. Suchcompounds are useful as, for example, materials for pharmaceuticals,agricultural chemicals, and other fine chemicals, and materials forfunctional polymers.

8. Production of Alcohols

By catalysis of the imide compound and where necessary in the presenceof oxygen, the alcohol represented by Formula (2) is allowed to reactwith the compound represented by Formula (12) having a methine carbonatom and thereby yields an alcohol represented by following Formula(17):

wherein R^(a), R^(b) R^(o), R^(p), R^(q) and Y have the same meanings asdefined above. This reaction can be performed pursuant to a process (aprocess using a catalytic 5-membered N-hydroxy cyclic imide compound)described in PCT International Publication No. WO00/35835.

The alcohols represented by Formula (2) include similar alcohols as inthe production of the 1,3-dihydroxy compounds. The compounds representedby Formula (12) having a methine carbon atom include similar compoundsas in the production of the hydroxy compounds. In this process, thecompound represented by Formula (12) having a methine carbon atom issupposed to serve as the radical scavenging compound (B2).

A reaction can be performed in accordance with the process of thepresent invention for producing an organic compound. Reaction productscan be separated and purified by the same separation means as above.

In this reaction, the alcohol represented by Formula (17) is supposed tobe formed in the following manner. A 1-hydroxyalkyl radicalcorresponding to the alcohol represented by Formula (2) is formed in asystem, attacks the methine carbon atom of the compound represented byFormula (12) and thereby yields the alcohol in question.

9. Production of Coupling Products

By catalysis of the imide compound and where necessary in the presenceof oxygen, a compound having a methine carbon atom and represented byfollowing Formula (12a):

wherein R^(o1), R^(p1) and R^(q1) are the same or different and are eachan organic group, where R^(o1), R^(p1) and R^(q1) may be combined witheach other to form a ring with the adjacent carbon atom, is allowed toreact with a compound having a methine carbon atom and represented byfollowing Formula (12b):

wherein R^(o2), R^(p2) and R^(q2) are the same or different and are eachan organic group, where R^(o2), R^(p2) and R^(q2) may be combined witheach other to form a ring with the adjacent carbon atom, and therebyyields a coupling product (a hydrocarbon) represented by followingFormula (18):

wherein R^(o1), R^(p1), R^(q1), R^(o2), R^(p2) and R^(q2) have the samemeanings as defined above. This reaction can be performed pursuant to aprocess (a process using a catalytic 5-membered N-hydroxy cyclic imidecompound) described in PCT International Publication No. WO00/35835.

In Formulae (12a) and (12b), the organic groups and preferred organicgroups in R^(o1), R^(p1), R^(q1), R^(o2) R^(p2), and R^(q2) includeorganic groups similar to those in R^(o), R^(p), and R^(q). The ringsformed by R^(o1), R^(p1), and R^(q1) (R^(o1) and R^(p1), R^(p1) andR^(q1), R^(q1) and R^(o1), or R^(o1) and R^(p1) and R^(q1)) with theadjacent carbon atom, and the rings formed by R^(o2), R^(p2), and R^(q2)(R^(o2) and R^(p2), R^(p2), and R^(q2), R^(p2) and R^(q2), or R^(o2) andR^(p2) and R^(q2)) with the adjacent carbon atom include rings similarto those formed by R^(o), R^(p), and R^(q) with the adjacent carbonatom.

The compounds represented by Formulae (12a) and (12b) each having amethine carbon atom include the compounds exemplified as the compounds(A3), such as the bridged cyclic compounds (A3-1a), the non-aromaticcyclic compounds (A3-1b) each having a hydrocarbon group combined with aring, and the chain compounds (A3-2) each having a methine carbon atom.The compound represented by Formula (12a) and the compound representedby Formula (12b) may be identical to, or different from, each other.

A reaction can be performed in accordance with the process of thepresent invention for producing an organic compound. Reaction productscan be separated and purified by the same separation means as above.

In this reaction, the coupling product represented by Formula (18) issupposed to be formed in the following manner. A radical is formed atthe methine carbon position of the compound represented by Formula(12a), attacks the methine carbon atom of the compound represented byFormula (12b) and thereby yields the coupling product in question.

10. Production of Carbonyl Compounds (2)

By catalysis of the imide compound and where necessary in the presenceof oxygen, an aldehyde represented by following Formula (19):R^(g)CHO  (19)wherein R^(g) is a hydrogen atom or an organic group, is allowed toreact with an olefin represented by following Formula (20):

wherein R^(c), R^(d), R^(e) and R^(h) are the same or different and areeach a hydrogen atom or an organic group, where R^(c), R^(d), R^(e) andR^(h) may be combined with each other to form a ring with the adjacentcarbon atom or carbon-carbon bond, and thereby yields a carbonylcompound represented by following Formula (21):

wherein R^(c), R^(d), R^(e), R^(h) and R^(g) have the same meanings asdefined above.

In Formula (19), the organic groups in R^(g) include similar organicgroups to those in R^(a) and R^(b). As the aldehyde represented byFormula (19), the aldehydes exemplified in the carbonyl-group-containingcompounds (A2-1) can be used.

In Formula (20), R^(c), R^(d) and R^(e) are the same as above, and theorganic groups in R^(h) include similar organic groups to those inR^(c), R^(d) and R^(e). As the olefin represented by Formula (20), thecompounds exemplified as the inert olefins (B1-6) and active unsaturatedcompounds (B1-1) can be used.

A reaction can be performed in accordance with the process of thepresent invention for producing an organic compound. Reaction productscan be separated and purified by the same separation means as above.

In this reaction, the carbonyl compound represented by Formula (21) issupposed to be formed in the following manner. A corresponding acylradical is formed from the compound represented by Formula (19), attacksthe carbon atom constituting the double bond of the compound representedby Formula (20) and thereby yields the carbonyl compound in question.

11. Production of β-Acyloxycarboxylic Acids or β-Acyloxyketones

By catalysis of the imide compound and in the presence of oxygen, thealcohol represented by Formula (2) is allowed to react with anα,β-unsaturated carbonyl compound represented by following Formula (22):

wherein R^(c) and R^(d) are the same or different and are each ahydrogen atom or an organic group; and R^(e1) and R^(r) are the same ordifferent and are each a hydrogen atom, a hydrocarbon group or aheterocyclic group, where R^(c) and R^(d) may be combined to form a ringwith the adjacent carbon atom, and thereby yields a β-acyloxycarboxylicacid or β-acyloxyketone represented by following Formula (23):

wherein Z is a hydroxyl group when R^(e1) in Formula (22) is a hydrogenatom, and Z is the substituent R^(e1) when R^(e1) is a hydrocarbon groupor a heterocyclic group; and R^(a), R^(b), R^(c), R^(d), and R^(r) havethe same meanings as defined above. This reaction can be performedpursuant to a process (a process using a catalytic 5-membered N-hydroxycyclic imide compound) described in Japanese Patent Application No.2000-648.

The organic groups, hydrocarbon groups, heterocyclic groups, and therings formed by R^(c) and R^(d) with the adjacent carbon atom includesimilar groups as mentioned above.

According to this reaction, for example, 2-propanol is allowed to reactwith methyl vinyl ketone and thereby yields 3-acetoxy-3-methylbutanoicacid. Likewise, 2-propanol is allowed to react with acrolein and therebyyields 3-formyloxy-3-methylbutanoic acid.

The reaction can be performed in accordance with the process of thepresent invention for producing an organic compound. Reaction productscan be separated and purified by the same separation means as above.

In this reaction, the target β-acyloxycarboxylic acid or β-acyloxyketonerepresented by Formula (23) is supposed to be formed in the followingmanner. A 1-hydroxyalkyl radical corresponding to the alcoholrepresented by Formula (2) is formed in the reaction system, attacks andis added to the beta-position of the α,β-unsaturated carbonyl compoundrepresented by Formula (22), oxygen attacks a radical formed at thealpha-position as a result of the addition and thereby yields anα,γ-dihydroxycarbonyl compound represented by following Formula (24):

wherein R^(a), R^(b), R^(c), R^(d), R^(e1) and R^(r) have the samemeanings as defined above. This compound further undergoes rearrangementof an acyl group (R^(r)C═O group) and oxidation of a carbon atom, towhich the acyl group has been bonded, and thereby yields the targetβ-acyloxycarboxylic acid or β-acyloxyketone represented by Formula (23).When an α,β-unsaturated carbonyl compound represented by Formula (22),where R^(e1) is a hydrogen atom, is used as the starting compound, acorresponding β-acyloxycarboxylic acid is formed. When anα,β-unsaturated carbonyl compound represented by Formula (22), whereR^(e1) is a hydrocarbon group or heterocyclic group, is used as thestarting compound, a corresponding β-acyloxyketone is formed.

12. Production of Polyacrylamide Polymers

In the presence of the imide compound and the compound (A) capable offorming a radial, an α,β-unsaturated carboxylic acid amide ispolymerized under mild conditions and thereby yields a correspondingpolyacrylamide polymer [refer to Japanese Patent Application No.2000-345822 (a process using a catalytic 5-membered N-hydroxy cyclicimide compound)].

Typical examples of the α,β-unsaturated carboxylic acid amide are(meth)acrylamide, N-methyl(meth)acrylamide,N,N-dimethyl(meth)acrylamide, N-isopropyl(meth)acrylamide,N-phenyl(meth)acrylamide, and crotonamide.

A reaction temperature can appropriately be selected depending on thetype of the raw material and other factors and is, for example, fromabout 0° C. to about 150° C. and preferably from about 10° C. to about100° C. By controlling the reaction temperature, the molecular weight ofthe resulting polymer can be controlled. The reaction product can beseparated and purified by, for example, precipitation orreprecipitation. 13. Production of Organic Compounds HavingOxygen-atom-containing Group

By catalysis of the imide compound, the compound (A) capable of forminga radical is allowed to react with the oxygen-atom-containing reactant(B4) and thereby yields an organic compound having anoxygen-atom-containing group.

This reaction is performed in the presence of, or in the absence of, asolvent. Such solvents include the aforementioned solvents. The amountof the catalytic imide compound is, for example, from about 0.0000001 toabout 1 mole, preferably from about 0.000001 to about 0.5 mole, morepreferably from about 0.00001 to about 0.4 mole, and often from about0.0001 to about 0.3 mole, relative to 1 mole of the compound (A). Thisreaction is significantly accelerated in many cases when a promoter suchas the metallic compound (e.g., vanadium compound, molybdenum compound,manganese compound or cobalt compound) is used in combination.

When the oxygen-atom-containing reactant (B4) is in the form of a gas,it maybe diluted with an inert gas such as nitrogen gas or argon gas.Each of the oxygen-atom-containing reactants (B4) can be used alone orin combination. By using two or more types of the oxygen-atom-containingreactants (B4) in combination, two or more types of different functionalgroups can be introduced into the molecule. Such functional groupsinclude, for example, hydroxyl group, oxo group, carboxyl group, nitrogroup and sulfonic acid group. In the combination use, two types or moreof thee oxygen-atom-containing reactants (B4) can be used concurrentlyor sequentially.

The amount of the oxygen-atom-containing reactant (B4) depends on thetype thereof and can appropriately be selected in view of reactivity andoperability. For example, when oxygen (B4-1) is used as theoxygen-atom-containing reactant (B4), the amount of oxygen is equal toor more than about 0.5 mole (e.g., equal to or more than about 1 mole),preferably from about 1 to about 100 moles, and more preferably fromabout 2 to about 50 moles, relative to 1 mole of the compound (A).Oxygen is often used in excess to the compound (A).

When carbon monoxide (B4-2) and oxygen (B4-1) are used in combination asthe oxygen-atom-containing reactants (B4), carbon monoxide in an amountof equal to or more than about 1 mole (e.g., from about 1 to about 100moles) and oxygen in an amount of equal to or more than about 0.5 mole(e.g., from about 0.5 to about 50 moles) are often used relative to 1mole of the compound (A). In this case, the molar ratio of carbonmonoxide to oxygen is from about 1/99 to about 99.99/0.01, andpreferably from about 10/90 to about 99/1.

When the nitrogen oxide (B4-3) is used as the oxygen-atom-containingreactant (B4), the amount of the nitrogen oxide can appropriately beselected depending on the types of the nitrogen oxide and the compound(A) and may be equal to or more than 1 mole or may be less than 1 mole,relative to 1 mole of the compound (A). When the amount of the nitrogenoxide (e.g., nitrogen dioxide) is less than 1 mole (e.g., equal to ormore than about 0.0001 mole and less than 1 mole), preferably from about0.001 to about 0.8 mole, and more preferably from about 0.005 to about0.25 mole, relative to 1 mole of the compound (A), the conversion fromthe nitrogen oxide and the selectivity of the reaction can significantlybe improved.

By using nitrogen dioxide (NO₂) in combination with oxygen, the rate ofa reaction such as nitration reaction can be significantly improved. Inthis case, the amount of oxygen is equal to or more than about 0.5 mole(e.g., equal to or more than about 1 mole), preferably from about 1 toabout 100 moles, and more preferably from about 2 to about 50 moles,relative to 1 mole of nitrogen dioxide.

When the sulfur oxide (B4-4) is used as the oxygen-atom-containingreactant, the amount of the sulfur oxide can appropriately be selecteddepending on the types of the sulfur oxide and the compound (A) and isgenerally from about 1 to about 50 moles, and preferably from about 1.5to about 30 moles, relative to 1 mole of the compound (A). The reactioncan be performed in large excess of the sulfur oxide. When the sulfuroxide (e.g., sulfur dioxide) is used in combination with oxygen, themolar ratio of the sulfur oxide to the oxygen is, for example, fromabout 10/90 to about 90/10 and more preferably from about 30/70 to about70/30.

A reaction temperature can appropriately be selected depending on, forexample, the types of the compound (A) and the oxygen-atom-containingreactant. For example, when oxygen (B4-1) is used as theoxygen-atom-containing reactant, the reaction temperature is from about0° C. to about 300° C. and preferably from about 20° C. to about 250° C.

When carbon monoxide (B4-2) and oxygen (B4-1) are used as theoxygen-atom-containing reactants, the reaction temperature is, forexample, from about 0° C. to about 200° C. and preferably from about 10°C. to about 150° C. When the nitrogen oxide (B4-3) or sulfur oxide(B4-4) is used as the oxygen-atom-containing reactant (including thecase where oxygen is used in combination), the reaction temperature is,for example, from about 0° C. to about 150° C. and preferably from about10° C. to about 125° C. The reaction can be performed at atmosphericpressure or under a pressure (under a load). When the reaction isperformed under a pressure, the pressure is generally from about 0.1 toabout 10 MPa, and preferably from about 0.2 to about 7 MPa. The reactioncan be performed in a conventional system such as a batch system,semi-batch system or continuous system.

After the completion of the reaction, reaction products can be separatedand purified by a technique such as filtration, concentration,distillation, extraction, crystallization, recrystallization,adsorption, column chromatography and other separation means, or anycombination of these separation means.

This process can produce a reaction product corresponding to theoxygen-atom-containing reactant in a high yield under mild conditions.

Specifically, when oxygen (B4-1) is used as the oxygen-atom-containingreactant, an oxidation reaction proceeds and thereby yields acorresponding oxidation product [refer to Japanese Unexamined PatentApplication Publications No. 8-38909, No. 9-327626, No. 10-286467, andNo. 2000-219650 (processes using catalytic 5-membered N-hydroxy cyclicimide compounds)]. For example, when the heteroatom-containing compound(A1) having a carbon-hydrogen bond at the adjacent position to theheteroatom is used as the compound (A), a carbon atom at the adjacentposition to the heteroatom is oxidized. For example, a primary alcoholyields a corresponding aldehyde or carboxylic acid, and a secondaryalcohol yields a corresponding ketone. A 1,3-diol yields a correspondinghydroxyketone, and a 1,2-diol yields a corresponding a carboxylic acidas a result of oxidative cleavage [refer to Japanese Unexamined PatentApplication Publications No. 2000-212116 and NO. 2000-219652 (processesusing catalytic 5-membered N-hydroxy cyclic imide compounds)]. An etheryields a corresponding ester or acid anhydride [refer to JapaneseUnexamined Patent Application Publication No. 10-316610 (a process usinga catalytic 5-membered N-hydroxy cyclic imide compound)]. In addition, aprimary or secondary alcohol yields hydrogen peroxide [refer to PCTInternational Publication No. WO00/46145 (a process using a catalytic5-membered N-hydroxy cyclic imide compound)].

When the compound (A2) having a carbon-heteroatom double bond is used asthe compound (A), an oxidation product corresponding to the type of theheteroatom can be obtained. For example, by oxidizing a ketone, acarboxylic acid or another product is produced as a result of cleavage.For example, a cyclic ketone such as cyclohexanone yields a dicarboxylicacid such as adipic acid. By using the heteroatom-containing compound(A1) having a carbon-hydrogen bond at the adjacent position to theheteroatom, such as a secondary alcohol (e.g., benzhydrol), is used as aco-reactant (co-oxidizing agent), a Baeyer-Villiger type reactionproceeds under mild conditions. As a result, a cyclic ketone yields acorresponding lactone, and a chain ketone yields a corresponding esterin high yields [refer to PCT International Publication No. WO99/50204(cases where catalytic 5-membered N-hydroxy cyclic imide compounds areused)]. In addition, an aldehyde yields a corresponding carboxylic acid.

By using the compound (A3) having a methine carbon atom as the compound(A), an alcohol derivative having a hydroxyl group introduced into themethine carbon in a high yield. For example, by oxidizing a bridgedcyclic hydrocarbon (A3-1a) such as adamantane, alcohol derivatives eachhaving a hydroxyl group at a bridgehead position, such as 1-adamantanol,1,3-adamantanediol and 1,3,5-adamantanetriol, can be produced with highselectivity. The chain compound (A3-2) having a methine carbon atom,such as isobutane, can yield a tertiary alcohol such as t-butanol in ahigh yield [refer to Japanese Unexamined Patent Application PublicationNo. 10-310543 (a process using a catalytic 5-membered N-hydroxy cyclicimide compound)].

By using the compound (A4) having a carbon-hydrogen bond at the adjacentposition to an unsaturated bond as the compound (A), the adjacentposition to the unsaturated bond is efficiently oxidized and therebyyields, for example, an alcohol, carboxylic acid or ketone. For example,a compound having a methyl group at the adjacent position to anunsaturated bond yields a primary alcohol or carboxylic acid in a highyield [refer to Japanese Unexamined Patent Application Publications No.8-38909, No. 9-327626 and No. 11-106377 (processes using catalytic5-membered N-hydroxy cyclic imide compounds)]. Likewise, a compoundhaving a methylene group or methine group at the adjacent position to anunsaturated bond yields a secondary or tertiary alcohol, ketone orcarboxylic acid, depending on reaction conditions.

More specifically, an aromatic compound having an alkyl group or alower-order oxidized group thereof combined with an aromatic ring yieldsan aromatic carboxylic acid having a carboxyl group combined with thearomatic ring as a result of oxidation of the alkyl group or thelower-order oxidized group thereof. Such lower-order oxidized groupsinclude, for example, hydroxy alkyl groups, formyl group, formyl alkylgroups, and alkyl groups each having an oxo group. For example, benzoicacid is obtained from toluene, ethylbenzene, isopropylbenzene,benzaldehyde, or mixtures thereof; terephthalic acid is obtained fromp-xylene, p-isopropyltoluene, p-diisopropylbenzene, p-tolualdehyde,p-toluic acid, p-carboxybenzaldehyde, or mixtures thereof; isophthalicacid is obtained from m-xylene, m-tolualdehyde, m-carboxybenzaldehyde,or mixtures thereof; trimellitic acid is obtained from pseudocumene,dimethylbenzaldehyde, dimethylbenzoic acid, or mixtures thereof;pyromellitic acid is obtained from durene, trimethylbenzaldehyde,trimethylbenzoic acid, or mixtures thereof; 3-quinolinecarboxylic acidis obtained from, for example, 3-methylquinoline, respectively in highyields. In addition, nicotinic acid is obtained from β-picoline.

For example, a compound having a methylene group at the adjacentposition to a carbon-carbon double bond yields a secondary alcohol orketone. In this case, by using a cobalt (II) salt of an acid having apKa of less than or equal to 8.0, such as cobalt(II) acetate orcobalt(II) nitrate, is used as the promoter, a corresponding conjugatedunsaturated carbonyl compound having an oxo group introduced into thecarbon atom of the methylene group can be obtained in a high yield. Morespecifically, valencene yields nootkatone in a high yield.

By using the non-aromatic cyclic hydrocarbon (A5) as the compound (A),an alcohol, hydroperoxide or ketone having a hydroxyl group, hydroperoxygroup or oxo group introduced into a carbon atom constituting a ring isobtained. Under some reaction conditions, the ring is oxidativelycleaved and yields a corresponding dicarboxylic acid. For example, byappropriately selecting the conditions, cyclohexane can yield cyclohexylalcohol, cyclohexyl hydroperoxide, cyclohexanone or adipic acid withhigh selectivity. Likewise, a cycloalkane such as cyclohexane yields abis(1-hydroxycycloalkyl)peroxide such asbis(1-hydroxycyclohexyl)peroxide [refer to Japanese Patent ApplicationNo. 2000-345824 (a process using a catalytic 5-membered N-hydroxy cyclicimide compound)]. By using a strong acid as the promoter, adamantane canyield adamantanone in a high yield [refer to Japanese Unexamined PatentApplication Publication No. 10-309469 (a process using a catalytic5-membered N-hydroxy cyclic imide compound)].

When the conjugated compound (A6) is used as the compound (A), a varietyof compounds is formed depending on the structure of the conjugatedcompound. For example, a conjugated diene yields an alkenediol or otherproducts as a result of oxidation. Specifically, butadiene yields, forexample, 2-butene-1,4-diol and/or 1-butene-3,4-diol as a result ofoxidation. When an α,β-unsaturated nitrile or α,β-unsaturated carboxylicacid or a derivative thereof is oxidized, the α,β-unsaturated bondingposition is selectively oxidized and is converted into a single bond,and the beta-position is converted into a formyl group, an acetal group(when the reaction is performed in the presence of an alcohol) or anacyloxy group (when the reaction is performed in the presence of acarboxylic acid) in the resulting compound. More specifically, byoxidizing acrylonitrile and methyl acrylate in the presence of methanol,3,3-dimethoxypropionitrile and methyl 3,3-dimethoxypropionate arerespectively formed.

When the amine (A7) is used as the compound (A), a corresponding Schiffbase or oxime is formed. When the aromatic compound (A8) is used as thecompound (A) in the co-existence of, for example, the compound (A4)having a carbon-hydrogen bond at the adjacent position to an unsaturatedbond (e.g., fluorene) as the co-reactant (co-oxidizing agent), acorresponding quinone is formed in a good yield [refer to JapaneseUnexamined Patent Application Publications No. 11-226416 and No.11-228484 (processes using catalytic 5-membered N-hydroxy cyclic imidecompounds)]. The straight-chain alkane (A9) yields, for example, analcohol, ketone or carboxylic acid.

By using the olefin (A10) as the compound (A), a corresponding epoxycompound can be obtained [refer to Japanese Unexamined PatentApplication Publication No. 11-49764 and PCT International PublicationNo. WO99/50204 (processes using catalytic 5-membered N-hydroxy cyclicimide compounds)]. Specifically, when the heteroatom-containing compound(A1) having a carbon-hydrogen bond at the adjacent position to theheteroatom, such as a secondary alcohol, or the compound (A4) having acarbon-hydrogen bond at the adjacent position to an unsaturated bond isused as the co-reactant (co-oxidizing agent), an epoxidation reactionproceeds under mild conditions and thereby yields the correspondingepoxide in a good yield.

By allowing at least one compound selected from cycloalkanes,cycloalkanols and cycloalkanones to react with ammonia and oxygen (B4-1)as the oxygen-atom-containing reactant in the presence of the catalyticimide compound, a corresponding lactam is obtained [refer to JapanesePatent Application No. 2000-345823 (a process using a catalytic5-membered N-hydroxy cyclic imide compound)]. More specifically, byallowing at least one compound selected from cyclohexane, cyclohexanoland cyclohexanone to react with ammonia and oxygen in the presence ofthe catalyst, ε-caprolactam is obtained.

By using carbon monoxide (B4-2) and oxygen (B4-1) as theoxygen-atom-containing reactants, a carboxylation reaction smoothlyproceeds and thereby yields a corresponding carboxylic acid in a goodyield [refer to Japanese Unexamined Patent Application Publication No.11-239730 (a process using a catalytic 5-membered N-hydroxy cyclic imidecompound)]. For example, when the compound (A3) having a methine carbonatom is used as the compound (A), a carboxyl group is introduced intothe methine carbon atom. Likewise, in the compound (A4) having acarbon-hydrogen bond at the adjacent position to an unsaturated bond, acarboxyl group is introduced into a carbon atom relating to thecarbon-hydrogen bond. The non-aromatic cyclic hydrocarbon (A5), such ascyclohexane, yields a carboxylic acid having a carboxyl group combinedwith a carbon atom constituting a ring.

When the nitrogen oxide (B4-3) is used as the oxygen-atom-containingreactant, a nitration reaction predominantly proceeds and therebyyields, for example, a corresponding nitro compound [refer to JapaneseUnexamined Patent Application Publication No. 11-239730 (a process usinga catalytic 5-membered N-hydroxy cyclic imide compound)]. For example,when the compound (A3) having a methine carbon atom is used as thecompound (A), the methine carbon atom is nitrated. Likewise, when thecompound (A4) having a carbon-hydrogen bond at the adjacent position toan unsaturated bond is used, a carbon atom relating to thecarbon-hydrogen bond is nitrated. The non-aromatic cyclic hydrocarbon(A5), such as cyclohexane, yields a corresponding cyclic nitro compoundhaving a nitro group combined with a carbon atom constituting a ring.Even the straight-chain alkane (A9), such as hexane, can yield acorresponding nitroalkane. When nitrogen dioxide is used as theoxygen-atom-containing reactant, the nitration reaction can efficientlyproceed by using the substrate in excess to nitrogen dioxide [refer toJapanese Unexamined Patent Application Publication No. 11-136339 (aprocess using a catalytic 5-membered N-hydroxy cyclic imide compound)].

When a compound having a methyl group at the adjacent position to anaromatic ring (at the “benzyl position”), such as toluene, is used asthe compound (A), a nitro group is introduced into the carbon atom ofthe methyl group. Under some conditions, the methyl group is convertedinto a formyl group and thereby yields a corresponding aromatic aldehyde(e.g., benzaldehyde), or a nitro group is introduced into the aromaticring in the resulting compound. The use of a compound having a methylenegroup at the adjacent position to an aromatic ring (e.g., ethylbenzene)as the substrate yields a nitro compound (e.g., α-nitrobenzene), inwhich the methylene group is nitrated, and under some reactionconditions, yields an oxime compound (e.g., acetophenone oxime) wherethe methylene group is converted into an oxime.

By using nitrogen monoxide as the oxygen-atom-containing reactant, anether can yield a corresponding aldehyde as a result of cleavage of theether bond [Japanese Unexamined Patent Application Publications No.11-315036 and No. 11-254977 (processes using catalytic 5-memberedN-hydroxy cyclic imide compounds)]. For example, phthalan can yieldphthalaldehyde in a high yield. Likewise, by using nitrogen monoxide asthe oxygen-atom-containing reactant, a cycloalkane yields acorresponding cycloalkanone oxime [refer to Japanese Patent ApplicationNo. 2000-157356 (a process using a catalytic 5-membered N-hydroxy cyclicimide compound)]. For example, cyclohexane yields cyclohexanone oxime.

By allowing a chain or cyclic compound having a methylene group to reactwith the nitrogen oxide such as nitrogen monoxide in the presence of thecatalytic imide compound and a halogen (e.g., chlorine) or a Beckmannrearrangement catalyst, a corresponding amide or lactam is obtained[refer to Japanese Patent Application No. 11-372177 (a process using acatalytic 5-membered N-hydroxy cyclic imide compound)]. For example,cyclohexane yields ε-caprolactam.

When the nitric acids are used as the oxygen-atom-containing reactant, anitration reaction predominantly proceeds and thereby yields, forexample, a corresponding nitro compound, as in the use of the nitrogenoxide (B4-3) [refer to Japanese Patent Application No. 2000-58054 (aprocess using a catalytic 5-membered N-hydroxy cyclic imide compound)].For example, when the compound (A4) having a carbon-hydrogen bond at theadjacent position to an unsaturated bond is used as the substrate, acarbon atom relating to the carbon-hydrogen bond is nitrated. When thecompound (A3) having a methine carbon atom is used as the substrate, themethine carbon atom is nitrated. When the non-aromatic cyclichydrocarbon (A5) is used as the substrate, a nitro group is introducedinto a carbon atom constituting a ring. In this case, acycloalkane, suchas cyclohexane, yields a corresponding nitrocycloalkane. In thenon-aromatic heterocyclic compound having a carbon-hydrogen bond at theadjacent position to the heteroatom, a carbon atom relating to thecarbon-hydrogen bond is nitrated. Likewise, the straight-chain alkane(A9), such as hexane, yields a corresponding nitroalkane. This reactionis supposed to proceed in the following manner. The imide compoundreacts with the nitric acids and thereby yields an imido-N-oxy radical,the radical withdraws a hydrogen atom from the substrate and therebyyields another radical, and to the resulting radical, nitrogen dioxideformed in the reaction system is added and thereby yields acorresponding nitro compound.

When the sulfur oxide (B4-4) is used as the oxygen-atom-containingreactant, a sulfonation and/or sulfination reaction proceeds and therebyyields a corresponding organic sulfur acid or a salt thereof. Forexample, when the compound (A3) having a methine carbon atom is used asthe compound (A), a sulfur acid group is introduced into the methinecarbon atom. When the compound (A4) having a carbon-hydrogen bond at theadjacent position to an unsaturated bond is used, a sulfur acid group(e.g., a sulfonic acid group or sulfinic acid group) is introduced intoa carbon atomrelating to the carbon-hydrogen bond. The non-aromaticcyclic hydrocarbon (A5), such as cyclohexane, yields an organic sulfuracid having a sulfur acid group combined with a carbon atom constitutinga ring. The formed organic sulfur acid can be converted into acorresponding salt thereof according to conventional techniques. Forexample, the salt can be obtained by reacting the organic sulfur acidwith an alkali metal hydroxide, alkali metal carbonate, alkali metalhydrogencarbonate, alkaline earth metal hydroxide, alkaline earth metalcarbonate, amine, thiourea, or isothiourea in an appropriate solventsuch as water.

INDUSTRIAL APPLICABILITY

The present invention can produce, for example, organic compounds eachhaving an oxygen-atom-containing group such as hydroxyl group, oxogroup, carboxyl group, nitro group or sulfonic acid group, products as aresult of the formation of a carbon-carbon bond or derivatives thereof(e.g., cyclized derivatives) with high selectivity in high yields as aresult of addition or substitution reactions under mild conditions. Inaddition, the present invention can introduce such anoxygen-atom-containing group into an organic substrate under mildconditions.

The catalyst of the present invention is highly stable and can maintainits catalytic activity for a long time. The catalyst exhibits highcatalytic activity even in a small amount in a radical reaction and ishighly stable in a reaction at high temperatures.

EXAMPLES

The present invention will be illustrated in further detail withreference to several examples below, which are not intended to limit thescope of the invention. Reaction products were identified by NMR, IRand/or GC-MS.

Preparation Example 1

Production of N-hydroxynaphthalimide

A 3-L flask equipped with a stirrer, cooling tube and thermometer waspurged by nitrogen gas. 55.2 g (770 mmol) of hydroxylamine-hydrochloride(purity of 97%) and 1.2 L of pyridine were added to the flask and werestirred to dissolve at room temperature under nitrogen atmosphere. Tothe stirred mixture, 138.7 g (700 mmol) of 1,8-naphthalenedicarboxylicanhydride was added. The stirred mixture was heated at 40° C. for 1 hourand subsequently was heated at 70° C. for 1 hour. After stirring at 90°C. for 1 hour, the reaction mixture was cooled to room temperature withstirring. The resulting crystalline solid was filtered off and washedwith 5% by weight of acetic acid aqueous solution and dried at 80° C.for 20 hours under a reduced pressure to yield 120.7 g (81%) ofN-hydroxynaphthalimide with yellow color.

Spectral Data

¹H-NMR (DMSO-d6, 500 MHz) δ: 7.8–8.0 (m, 2H, ArH), 8.4–8.6 (m, 4H, ArH),10.74 (brs, 1H, OH)

¹³C-NMR (DMSO-d6, 125 MHz) δ: 160.8, 134.6, 131.4, 130.8, 127.3, 126.2,122.3

MS (FAB⁺) m/z 214 ((M+H)⁺, 100), 177 (8), 85 (12)

Preparation Example 2

Production of N-acetoxynaphthalimide(N-acetoxy-1,8-naphthalenedicarboximide)

A 1-L flask equipped with a stirring, cooling tube, thermometer anddropping funnel was purged by nitrogen gas. 80.0 g (375 mmol) ofN-hydroxynaphthalimide obtained by preparation example 1 and 200 ml ofacetic acid were added to the flask. The stirred mixture was heated at60° C. under nitrogen atmosphere. To the resulting mixture, 76.7 g (750mmol) of acetic anhydride was added dropwise for 20 minutes. Afterstirring at 110° C. for 1.5 hours, the reaction mixture was cooled toroom temperature with stirring. The crystalline solid was filtered offand washed with acetic acid, and dried at 80° C. for 12 hours under areduced pressure to yield 82.6 g (86%) of N-acetoxynaphthalimide withpale yellow color.

Spectral Data

¹H-NMR (CDCl₃, 500 MHz) δ: 2.48 (s, 3H, CH₃), 7.7–7.8 (m, 2H, ArH),8.2–8.3 (m, 2H, ArH), 8.5–8.7 (m, 2H, ArH)

¹³C-NMR (CDCl₃, 125 MHz) δ: 166.6, 159.4, 135.0, 131.8, 131.7, 127.4,127.0, 122.1, 17.8

MS (FAB⁺) m/z 256 ((M+H)⁺, (66)), 214 (100), 198 (12)

Preparation Example 3

Production of N,N′-dihydroxy-1,8;4,5-naphthalenetetracarboxdiimide

A 5-L flask equipped with a stirrer, cooling tube and thermometer waspurged by nitrogen gas. 110.3 g (1.54 mol) ofhydroxylamine-hydrochloride (purity of 97%) and 2 L of pyridine wereadded to the flask and were dissolved with stirring at room temperatureunder nitrogen atmosphere. To the stirred mixture, 187.7 g (700 mmol) of1,8;4,5-naphthalenetetracarboxylic dianhydride was added. The stirredmixture was heated at 40° C. for 1 hour and subsequently was heated at70° C. for 1 hour. After stirring at 90° C. for 1 hour, the reactionmixture was cooled to room temperature with stirring. The precipitatewas filtered off, washed with 5% by weight of acetic acid aqueoussolution, and dried at 80° C. for 12 hours under a reduced pressure toyield 160.1 g (69%) ofN,N′-dihydroxy-1,8;4,5-naphthalenetetracarboxdiimide with brown color.

Spectral Data

¹H-NMR (DMSO-d6, 500 MHz) δ: 8.5–8.7 (m, 4H, ArH), 11.01 (brs, 2H, OH)

¹³C-NMR (DMSO-d6, 125 MHz) δ: 160.1, 130.6, 126.9, 125.3

MS (FAB⁺) m/z 299 ((M+H)⁺, (100)), 283 (23), 232 (7), 177 (7), 140 (5)

Preparation Example 4

Production of N,N′-diacetoxy-1,8;4,5-naphthalenetetracarboxdiimide

A 2-L flask equipped with a stirring, cooling tube, thermometer anddropping funnel was purged by nitrogen gas. 89.4 g (300 mmol) ofN,N′-dihydroxy-1,8;4,5-naphthalenetetracarboxdiimide obtained bypreparation example 3, 400 ml of acetic acid and 122.6 g (1.2 mol) ofacetic anhydride were added to the flask. The stirred mixture was heatedat 100° C. for 1 hour under nitrogen atmosphere. After stirring at 120°C. for 4 hours, the reaction mixture was cooled to room temperature withstirring. The resulting precipitate was filtered off and washed withacetic acid, and dried at 80° C. for 12 hours under a reduced pressureto yield 107.4 g (94%) ofN,N′-diacetoxy-1,8;4,5-naphthalenetetracarboxdiimide with ocher color.

Spectral Data

¹H-NMR (DMSO-d6, 500 MHz, 120° C.) δ: 2.47 (s, 6H, CH₃), 8.7–8.9 (m, 4H,ArH)

¹³C-NMR (DMSO-d6, 125 MHz, 120° C.) δ: 165.9, 157.5, 130.9, 126.2,125.7, 16.6

MS (FD⁺) m/z 382 (M⁺, (100)), 339 (42), 296 (31), 43 (94)

Example 1

In a 500-ml titanium autoclave equipped with a stirrer and a pressuregauge, 12.00 g of p-xylene, 107.03 g of acetic acid, 0.576 g ofN-acetoxy-1,8-naphthalenedicarboximide obtained by preparation example 2(2% by mole relative to p-xylene), 0.112 g of cobalt(II) acetate.4 H₂Oand 0.277 g of manganese(II) acetate.4 H₂O were placed. The autoclavewas charged with 3 MPa of oxygen gas and 2 MPa of nitrogen gas andplaced in a heated oil bath. The mixture was stirred at 150° C. for 4hours. After the completion of the reaction, the autoclave was placed oncold water to cool down the reaction mixture quickly. The resultingmixture was analyzed by high performance liquid chromatography and wasfound to yield terephthalic acid in 89% yield at 100% conversion ofp-xylene.

Example 2

In a 500-ml titanium autoclave equipped with a stirrer and a pressuregauge, 12.00 g of p-xylene, 107.03 g of acetic acid, 0.144 g ofN-acetoxy-1,8-naphthalenedicarboximide obtained by preparation example 2(0.5% by mole relative to p-xylene), 0.112 g of cobalt(II) acetate.4 H₂Oand 0.277 g of manganese(II) acetate.4 H₂O were placed. The autoclavewas charged with 2 MPa of oxygen gas and 2 MPa of nitrogen gas andplaced in a heated oil bath. The mixture was stirred at 150° C. for 1hour. After the completion of the reaction, the autoclave was placed oncold water to cool down the reaction mixture quickly. To the resultingreaction mixture, 0.144 g of N-acetoxy-1,8-naphthalenedicarboximideobtained by preparation example 2 was added. The autoclave was chargedwith 2 MPa of oxygen gas and 2 MPa of nitrogen gas and placed in aheated oil bath. The mixture was stirred at 150° C. for 1 hour. Afterthe completion of the reaction, the autoclave was placed on cold waterto cool down the reaction mixture quickly. Furthermore, a series of theabove operation of from the addition ofN-acetoxy-1,8-naphthalenedicarboximide to cooling down was repeatedtwice. The resulting mixture was analyzed by high performance liquidchromatography and was found to yield terephthalic acid in 94% yield at100% conversion of p-xylene.

Example 3

The procedure of Example 1 was repeated, except that reactiontemperature was 190° C., and thereby yielded terephthalic acid in 97%yield at 100% conversion of p-xylene.

Comparative Example 1

The procedure of Example 1 was repeated, except that 3.07 g ofN-hydroxyphthalimide (20% by mole relative to p-xylene) was used insteadof N-acetoxy-1,8-naphthalenedicarboximide, and thereby yieldedterephthalic acid in 59% yield at 93% conversion of p-xylene.

Example 4

In a 500-ml titanium autoclave equipped with a stirrer, 15.36 g ofp-toluic acid, 104.0 g of acetic acid, 0.288 g of obtained bypreparation example 2 (1% by mole relative to p-toluic acid), 0.112 g ofcobalt(II) acetate.4 H₂O and 0.277 g of manganese(II) acetate.4 H₂O wereplaced. The inside pressure was increased using 2 MPa of oxygen gas and2 MPa of nitrogen gas. The temperature of the resulting mixture waselevated on an oil bath and was held at 150° C. with stirring for 1hour. After the completion of the reaction, the autoclave was placed oncold water to cool down the reaction mixture quickly. The resultingsolution was analyzed by high performance liquid chromatography and wasfound to yield terephthalic acid in 83% yield at 88% conversion ofp-toluic acid.

Example 5

The procedure of Example 4 was repeated, except that a reactiontemperature was 190° C., and thereby yielded terephthalic acid in 94%yield at 96% conversion of p-toluic acid.

Comparative Example 2

The procedure of Example 5 was repeated, except that 0.184 g ofN-hydroxyphthalimide (1% by mole relative to p-toluic acid) was usedinstead of N-acetoxy-1,8-naphthalenedicarboximide, and thereby yieldedterephthalic acid in 45% yield at 50% conversion of p-toluic acid.

Example 6

The procedure of Example 4 was repeated, except that 0.216 g ofN,N′-diacetoxy-1,8;4,5-naphthalenetetracarboxdiimide (0.5% by molerelative to p-toluic acid) was used instead ofN-acetoxy-1,8-naphthalenedicarboximide, and thereby yielded terephthalicacid in 88% yield at 93% conversion of p-toluic acid.

Example 7

The procedure of Example 6 was repeated, except that a reactiontemperature was 190° C., and thereby yielded terephthalic acid in 90%yield at 92% conversion of p-toluic acid.

Example 8

In a 1L titanium autoclave equipped with a stirrer, a cooling tube, amass flow and a pressure controller, 80.00 g of β-picoline, 311.3 g ofacetic acid, 6.58 g of N-acetoxy-1,8-naphthalenedicarboximide obtainedby preparation example 2 (3% by mole relative to β-picoline), 1.070 g ofcobalt(II) acetate.4 H₂O and 1.053 g of manganese(II) acetate. 4 H₂Owere placed. The reaction mixture was controlled to the temperature at140° C. and the pressure of 10 kgf/cm² [0.98 MPa (gauge pressure)] underflow of air into the autoclave and the reaction was performed for 3hours. The resulting product in the reaction mixture was analyzed by gaschromatography and was found to yield nicotinic acid in 66% yield at 73%conversion of β-picoline.

Example 9

The procedure of Example 2 was repeated, except that 12.00 g of m-xylenewas used instead of p-xylene, and thereby yielded isophthalic acid in95% yield at 100% conversion of m-xylene.

Example 10

The procedure of Example 9 was repeated, except that a reactiontemperature was 190° C., and thereby yielded isophthalic acid in 97%yield at 100% conversion of m-xylene.

Example 11

A mixture of 1.00 g of fluorene, 0.154 g ofN-acetoxy-1,8-naphthalenedicarboximide obtained by preparation example 2(10% by mole relative to fluorene), 9.0 g of acetic acid, 0.008 g ofcobalt(II) acetate.4 H₂O and 0.008 g of manganese(II) acetate.4 H₂O wasstirred at 120° C. in an atmosphere of oxygene gas (1 atm=0.1 MPa) for 6hours. The resulting product in the reaction mixture was analyzed by gaschromatography and was found to yield fluorenon in 82% yield at 96%conversion of fluorene.

Example 12

A mixture of 1.00 g of cyclohexane, 0.152 g ofN-acetoxy-1,8-naphthalenedicarboximide obtained by preparation example 2(5% by mole relative to cyclohexane), 0.015 g of cobalt(II) acetate.4H₂O and 0.015 gofmanganese(II) acetate.4 H₂O was stirred at 100° C. inan atmosphere of oxygene gas (1 atm=0.1 MPa) for 8 hours. The resultingproduct in the reaction mixture was analyzed by gas chromatography andwas found to yield cyclohexanon, adipic acid and glutaric acid in 1%, 6%and 1% yields, respectively, at 12% conversion of cyclohexane.

Example 13

In a 500-mL titanium autoclave equipped with a stirrer and a pressuregauge, 12.00 g of 4-nitrotoluene, 107.03 g of acetic acid, 0.670 g ofN-acetoxy-1,8-naphthalenedicarboximide obtained by preparation example 2(3% by mole relative to 4-nitrotoluene), 0.087% of cobalt(II) acetate.4H₂O and 0.215 g of manganese(II) acetate.4 H₂O were placed. Theautoclave was charged with 2 MPa of oxygen gas and 2 MPa of nitrogen gasand placed in a heated oil bath. The mixture was stirred at 170° C. for1 hour. After the completion of reaction, the autoclave was placed oncold water to cool down the reaction mixture quickly. The resultingmixture was analyzed by high performance liquid chromatography and wasfound to yield 4-nitrobenzoic acid in 98% yield at 100% conversion of4-nitrotoluene.

Example 14

In a 500-mL titanium autoclave equipped with a stirred and a stirrer anda pressure gauge, 12.00 g of 4-bromotoluene, 107.22 g of acetic acid,0.537 g of N-acetoxy-1,8-naphthalenedicarboximide obtained bypreparation example 2 (3% by mole relative to 4-bromotoluene), 0.070 gof cobalt(II) acetate.4 H₂O and 0.175 g of manganese(II) acetate.4 H₂Owere placed. The autoclave was charged with 2 MPa of oxygen gas and 2MPa of nitrogen gas and placed in a heated oil bath. The mixture wasstirred at 170° C. for 1 hour. After the completion of reaction, theautoclave was placed on cold water to cool down the reaction mixturequickly. The resulting mixture was analyzed by high performance liquidchromatography and was found to yield 4-bromobenzoic acid in 95% yieldat 100% conversion of 4-bromotoluene.

Example 15

In a 500-mL titanium autoclave equipped with a stirrer and a pressuregauge, 12.00 g of 4-methylanisole, 106.91 g of acetic acid, 0.752 g ofN-acetoxy-1,8-naphthalenedicarboximide obtained by preparation example 2(3% by mole relative to 4-methylanisole), 0.098 g of cobalt(II)acetate.4 H₂O and 0.241 g of manganese(II) acetate.4 H₂O were placed.The autoclave was charged with 2 MPa of oxygen gas and 2 MPa of nitrogengas and placed in a heated oil bath. The mixture was stirred at 150° C.for 1 hour. After the completion of reaction, the autoclave was placedon cold water to cool down the reaction mixture quickly. The resultingmixture was analyzed by high performance liquid chromatography and wasfound to yield p-anisic acid and p-anisaldehyde in 85% and 5% yieldsrespectively at 100% conversion of 4-methylanisole.

Example 16

In a 500-mL titanium autoclave equipped with a stirrer and a pressuregauge, 12.00 g of 4-chlorotoluene, 106.95 g of acetic acid, 0.726 g ofN-acetoxy-1,8-naphthalenedicarboximide obtained by preparation example 2(3% by mole relative to 4-chlorotoluene), 0.095 g of cobalt(II)acetate.4 H₂O and 0.232 g of manganese(II) acetate.4 H₂O were placed.The autoclave was charged with 2 MPa of oxygen gas and 2 MPa of nitrogengas and placed in a heated oil bath. The mixture was stirred at 170° C.for 1 hour. After the completion of reaction, the autoclave was placedon cold water to cool down the reaction mixture quickly. The resultingmixture was analyzed by high performance liquid chromatography and wasfound to yield 4-chlorobenzoic acid in 96% yield at 100% conversion of4-chlorotoluene.

1. A catalyst composition comprising: an imide compound having anN-substituted cyclic imide skeleton represented by following Formula(1):

wherein R is a hydrolyzable hydroxyl-protecting group obtained from anacid by eliminating an OH group from the acid; R¹, R², R³, R⁴, R⁵ and R⁶are the same or different and are each a hydrogen atom, a halogen atom,an alkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, analkoxy group, a carboxyl group, a substituted oxycarbonyl group, an acylgroup, or an acyloxy group, wherein at least two of R¹, R², R³, R⁴, R⁵and R⁶ and may be combined with each other to form a double bond, anaromatic ring, or a non-aromatic ring, and wherein at least oneN-substituted cyclic imido group indicated by Formula (1) may further beformed on R¹, R², R³, R⁴, R⁵ and R⁶ or on the double bond, the aromaticring, or the non-aromatic ring formed by at least two of R¹, R², R³, R⁴,R⁵, and R⁶; in combination with a metallic compound, wherein the metalis selected from Groups 2 to 15 of the Periodic Table of Elements. 2.The catalyst composition according to claim 1, wherein the acid is oneselected from the group consisting of carboxylic acids, sulfonic acids,carbonic acid, carbamic acid, sulfuric acid, nitric acid, phosphoricacids, and boric acids.
 3. The catalyst composition according to claim1, wherein the imide compound of Formula (1) is selected from the groupconsisting of imides compound represented by following Formulas (1a),(1b), and (1c):

wherein R¹¹ to R¹⁶ are the same or different and are each a hydrogenatom, a halogen atom, an alkyl group, a aryl group, a cycloalkyl group,a hydroxyl group, an alkoxy group, a carboxyl group, a substitutedoxycarbonyl group, an acyl group, or an acyloxy group, and R¹⁷ to R²²are the same or different and are each a hydrogen atom, an alkyl group,a haloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group,a substituted oxycarbonyl group, an acyl group, a acyloxy group, a nitrogroup, a cyano group, an amino group, or a halogen atom, whereinadjacent groups of R¹⁷ to R²² may be combined to form a 6-memberedN-substituted cyclic imido skeleton indicated in Formula (1b) or (1c),its N-hydroxy form, a corresponding 5-membered N-substituted cyclicimido skeleton, or its N-hydroxy form, and R is as defined in claim 1.4. The catalyst composition according to claim 1, comprisingN-acetoxy-1,8-naphthalenedicarboximide, cobalt(II) acetate.4 H₂O, andmanganese (II) acetate.4 H₂O.